GB2057429A

GB2057429A - Herbicidal sulphonamides

Info

Publication number: GB2057429A
Application number: GB8023622A
Authority: GB
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1979-07-20
Filing date: 1980-07-18
Publication date: 1981-04-01
Also published as: ES493524A0; IL60631A; GB2057429B; CA1144923A; HU190668B; IE801495L; EP0070041A2; PT71580B; EP0023141A2; TR21772A; IE50022B1; ES8105274A1; AU536787B2; AU2489884A; BR8004382A; DK259280A; AU6060180A; DE3067433D1; EP0070041A3; IL60631A0

Abstract

Compounds of the formulae <IMAGE> wherein: A is selected from certain substituted amino, haloalkoxy or aryloxy groups; R1 is hydrogen, halogen, nitro or various organic groups; R'1 is H, Cl, F, Br, CH3 or OCH3; R4 and R5 are independently H or CH3 but not both CH3; R6 is a pyrimidyl or triazinyl residue which may be substituted; W is oxygen or sulfur; Z is CH or N; X1 and Y1 are H, CH3 or various alkoxy groups, but cannot both be H; and B is selected from various aliphatic or aromatic organic groups; and their agriculturally suitable salts, exhibit potent herbicidal activity. Some may also exhibit plant growth regulant activity. The compounds (I) can be made inter alia by reacting an isocyanate or isothiocyanate of general formula <IMAGE> with an amine NHR5R6. The compounds (I) can be converted into compounds (IA) by reacting an alkali metal or alkaline earth metal salt thereof with an appropriate halide BI or BBr. The intermediates (IB) can be made from the corresponding sulfonamide by various phosgenation reactions.

Description

1 GB 2 057 429 A 1

SPECIFICATION

Herbicidal sulfonamides, preparation and use thereof, compositions containing them, intermediates therefor and preparation of such intermediates This invention relates to certain benzene- 1 2-disuifonic acid derivatives that are useful as 5 agricultural chemicals.

French Patent No. 1,468,747 discloses the following para-substituted phenyisuifonamides, useful as anti-diabetic agents:

0 of N R SO 2 -NH-C-NH _ \ _W_ N wherein R = H, halogen, CF3 or alkyl.

Logemann et al., Chem. Ab., 53; 18052 g (1959), discloses a number of sulfonamides, including 10 uracil derivatives and those having the formula:

0 a 3 c -0- so 2 NWNHR wherein R is butyl, phenyl or N - _1 N 'i and R 1 R, is hydrogen or methyl. When tested for hypoglycemic effect in rats (oral doses of 25 mg/1 00 g), the 15 compounds in which R is butyl or phenyl were most potent. The others were of low potency or inactive. 15 Wojciechowski, J. Acta. Polon. Pharm. 19, P. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of W[(2,6-dimethoxypyri midi n-4-y1)a m inoca rbonyll-4-methyl benzenesu Ifona mide:

0 91 - CH SO NH-C-NH. N 3-C- 2 / OCR 3 OCR Based upon similarity to dknown compound, the author predicted hypoglycemic activity for the 20 foregoing compound.

Netherlands Patent 121,788, published September 15. 1966, teaches the preparation of compounds of Formula (i), and their use as general or selective herbicides:

0 N S02NHCN N R 4 2 N::

A3 wherein cl MR (i) R, and R2 may independently be alkyl of 1-4 carbon atoms; and R3 and R4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.

Compounds of Formula 00, and their use as anti-diabetic agents, are reported in J. Drug. Res. 6, 123 0974):

wherein R is pyridyl.

c1 0 -11 or S so 2 NHWHR The presence of undesired vegetation causes substantial damage to useful crops, especially 30 agricultural products that satisfy man's basic food needs, such as soybeans, wheat and the like.The current population explosion and concomitant world food shortage demand improvements in the 2 GB 2 057 429 A 2 efficiency of producing these crops. Prevention or minimizing the loss of a portion of such valuable crops by killing, or inhibiting the growth of undesired vegetation is one way of improving this efficiency.

A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need exists, however, for still more effective herbicides that destroy or retard weeds without causing significant damage to useful crops.

Summary of the Invention

This invention relates to novel compounds of Formulae 1 and IA, to agricultural compositions dbritaining them and their methods of use as general as well as selective pre- and post-emergence 10 herbicides and as plant growth regulants.

R1 so 2-A W 19 2-C-N-R6 R 4 k 5 R 1 so so 2 N=C-N]3- 0 Z (0_ N -J\ 2 A S-B N 1 R 1 wherein A is N1R,%, OCH2CC1, OCH,CBr, or 0 a OCH2CF2R. or Y 1 OCHRc 1 Ll-3 I IA where R,, isH,Cl, CH3, OCH3orNO2and Rbis H, ForCl-C2alkyl with 0-5F and Ft,isCH, orCF,;15 R1 is H, Cl, Br, F, Cl-C3 alkyl, N02, OCH3, 0 11 "-hdl CH,ORd, CF3, NH21 N=C=Q 0 0 0 11 11 11 MM-L-hd, imti-t--imHRd or NH-L-uhd where Rd'S Cl-C3 alkyl or R, is N(CH3)2, CK CH,S(O),CH3 or SOnCH31 where n is 0, 1 or 2; 20 R' is H, Cl, F, Br, CH3 or OCH3; R2 is H, Cl-C, alkyl, CJ__C4 alkenyl, Cg--C, cycloalkyl, C4---LC, cycloalkylalkyl, Cg--C, cyci6alkenyi, Cj-C, alkynyl, C17-C6 cycloalkyl substituted with 1-2 CH3 groups, CF2CF2H, CF2CHM, CF,CHMr, CF2CHFU,, C(CHICN, (CH2) CK where m is 1 or 2, CH,CH20CH31 CH2CH (CH)OCH,, (CH,), OCH3, CHR7C0,1R, or CHR7CON(RJ,, where R7 is H or CH3 and R,'S C,_C3 alkyl, OCH3, 77\ CHR -Q or OCHR 25 1 7 7 119 9 R 9 where R. is H, CH3, Cl, Br or F; R3 is Cl-C4 alkyl, C3-C4 alkenyl, CH2CH, OCH3, CH2CH(CH),0C1-13, CH2CF3, or (CH23),,,CK where m is 1 or 2, or CHRICOA, NR2R3 taken together are 3 GB 2 057 429 A 3 -N3 -N 0 or \--i R4 and RE, are independently H or CH3, but R4 and R, cannot both be CH3; R6 'S wherein X is H, CH3, CH30 or CH3CH20; Y X X N N N-N X.,?, - x z N or X, N --\/ r Y Y Y1 is Cl, Br, H, Cl-C, alkyl, CF3, NHCH3, N(CHI, OCH,CF3, OCH3, OCA, SCH3, O(CHjpOR,,, where p is 2 or 3 and R,, is CH3 or C,H,, CH,CH20CH3, CH20CH3, CH20CHCH3, OCHR7COA,, OCHR,CON(RJ2. COA, and CH2CO2Rll, where R,, is H or Cl-C, alkyl, CH,CN, NCH3(CH2CM, CH2CH,M, CH2C1, N3, OCH2CH=CH2 or OCH2C=CH; Xl is H, OCH, or CH3; Yl is H, OCH3, OCH,CH3 or CH., provided that X, and Yl are not both H simultaneously; Z is N or CH; W is 0 or S; and B is Cl-C, alkyl, CH2CH2OCH3, CH2CH2OCH2CH3, CH2CH2CH2OCH3, CH2G, CH-Q. 1 CH3 where G is C02-Cl-3 alkyl, 0 CH3 0 CN(C1-, alky02, -umrlkk'l-t'3 alkyl), -M 1 OCH3 0 Ii 0 CHN2, phenyl, phenyl substituted with chlorine, CN, C2-4 alkenyi, C2-4 alkynyi, 0%,, where OR', is 20 Cl-C4 alkyl, -CH20CH2CH2OCH3, or -CH20CH2CH2OCH2CH3; provided that: 1) when R2 is OCH3, R3 is CH.; 2) when R2 is CF2CHM, CF2CHFBr, CF2CF2H or CF2CHFU3, then R3'S C,_C4 alkyl; and their agriculturally suitable salts.

Preferred in order of increasing preference for reasons of increased activity or ease of synthesis, or both,are (1) Compounds of Formula 1. (2) Compounds of preference-(1), wherein R4 = Rr, = H. 30 (3) Compounds of preference (2), wherein W = 0. (4) Compounds of preference (3), wherein R' = H. (5) Compounds of preference (4), wherein R6 is N / z N =-\/ Y (6) Compounds of preference (5), wherein A is OCH2CF3 or NR2R. and R2 is Cl-C, alkyl, C--C4 alkenyi, OCH3, CH2CH2OCH,, CH2CH(CH.)OCH, or (CH2)30CH., or NR2R, taken together are 35 4 GB 2 057 429 A 4 -N), -1) r -N 0 or -0 (7) Compounds of preference (5), wherein R3 'S Cl-C4 alkyl or where NR,R3 taken together are -N] -N 0 or 1 -N / OCH 3 \ CH 3 (8) Compounds of preference (6), wherein R3 'S Cl-C4 alkyl or where NR2R.. taken together are (11) Compounds of preference (10) in which X is CH3, OCH3 or OCH2CH3; and Y is H, CH3, CH3CH2, OCH2CF3, OCH3, OCA, OCHPI.OCH3, CH20CH3, CH2CH2OCH3, N(CH)CH2M OCH2CH=CH., or OCH2C=_CH. (12) Compounds of preference (11) in which X is CH3, OCH3 or OCH2CH3; and 15 Y is CH3, OCH2CF3, OCH3 or OCH2CH3. Specifically preferred for their high biological activity or favorable ease of synthesis, or both, are N'-[(4,6-Dimethoxypyri midin-2- y1)a m inoca rbonyll-N,N-di methyl- 1 2-benzenedisuifona mide. N'-[(4,6- Dimethoxy- 1 3,5-triazin-2-yi)a m inocarbonyll-N, N-di methyl- 1, 2benzenedisu Ifona mide. NI-[(4-Methoxy-6-methylpyrimidin-2- yi)aminocarbonyll-N,N-di methyl1,2-benzenedisuifonamide. 20. N'-[(4- Methoxy-6-methyi- 1,3,5-triazi n-2-y1)am inoca rbonyll-N,N-di methyl- 1 2 -benzenedisulfona mide. 20 W4K6-Di methyl- 1,3,5-triazin-2-yi)aminoca rbonyll-N,N-di methyl-1,2-benzenedisuifonamide. N'-[(4,6- Dimethylpyrimidin-2-yi)a minocarbonyll-N,N-di methyl- 1,2- benzenedisuifona mide. N'-[(4-Methoxy-6-methylpyrimidin-2yi)aminocarbonyll-N,N-diethyl-1,2-benzene disuifonamide. N'-[(4,6Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyll-N,N-diethy]-1,2-benzene disuifonamide.

N'-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyll-N,N-diethyl-l,2benzenedisui fonamide. N'-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyll-N,Ndiethyi-1,2-benzenedisuif onamide. N'-[(4-Methoxy-6-methyl-1,3,5-triazin2-yi)aminocarbonyll-N,N-diethy]-1,2-be nzenedisuifonamide. N'-[(4,6Dimethyi-1,3,5-triazin-2-yi)aminocarbonyll-N,N-diethyl-1,2-benzened isuifonamide. N14(4,6-Di methoxypyrimidi n-2-y1)a m inoca rbonyll-N I,Nldi methyl-4-(trifl uorom ethyl)- 1 2- benzenesuffonamide. 4-Chloro-N 2-[(4-methoxy-6-methyl pyri midi n-2-yl)a mi noca rbonyll-N I,N 1-di methyl- 1,2benzenedisuffonamide. (2,2,2- Trifluoroethyl) 2-[[(4,6-dimethoxypyrimidin2yi)aminocarbonyllaminosuifonyllbenzenesuifonoat e.

(2,2,2-Trifluoroethyi) 2-[[(4,6-dimethoxy-1,3,5-triazin2yi)aminocarbonyllaminosuffonyllbenzenesulfonoate. (2,2,2-Trifluoroethyl) 2-[[(4-methoxy-6-m ethyl pyri m idin2yl)aminocarbonyllaminosuifonyllbenzenesuifonoate. (2,2,2Trifluoroethyi) 2-[[(4-methoxy-6-methyl-1,3,5-triazin-2yi)aminocarbonyllamidosuifonyllbenzenesuifonoate. N'[(F4,6Dimethylpyrimidin-2yi)aminocarbonyll-N-ethyi-N-methy]-1,2-benzened isuifonamide. N-Ethyi-N'-[(4-methoxy-6-methylpyrimidin-2yi)aminocarbonyll-N-methy]-1,2-be nzendisuifonamide. N'-[(4,6Dimethoxypyrimidin-2-yi)aminocarbonyll-N-ethyi-N-methyi-1,2-benzene disuifonamide. 4-Ch loro-NI -[(4-m ethoxy-6-methyl- 1,3,5-triazi n-2-yl) a mi noca rbonyll-N, N-di methyl- 1 2- benzenedisuifonamide. N,N-Dimethyi-N'-(([4-methyf-6-(2,2,2trifluoroethoxy)-1,3,5-triazin-2-yilami nocarbonyi))-1, 2benzendisulfonamide.

r---\ -N].0 -N0 or -1,4, OCH 3 CH 3 (9) Compounds of preference (8), wherein R, is H, Cl, CF3, N02, CH3 or OCH3. (10) Compounds of preference (9), wherein R2 is Cl-C, alkyl or NR2R3 taken together are /1" -N or -N 0 3 rp 1 1 lz 25:# A j wherein A is NR 2133, OCH2CC13, OCH2Wr3, OCH2CIFA or GB 2 057 429 A 5 N-Methyl-N(1 -methyl ethyl)-N'-[(4,6-di methoxypyrimidin-2-yi)a minocarbonyll- 12benzenedisulfonamide. N-Methyl-N(1 -methylethyi)-N'-[(4methyl-6-methoxypyrimidin-2-yi)aminocarbonyl1-1,2benzenedisulfonamide. NMethyA[1 -methylethyi)-N'-[4-methyi-6-methoxy-1,3,5-triazin-2yi)aminocarbonyll-1,2benzenedisuffonamide.

This invention also relates to novel suffonylisocyanate intermediates of Formula 1-B so 2 A Ri C so 2 N=C=W R 1 1-B 0 R a OCHRc 1 U 1-3 where R. is H, Cl, CH3, OCH3 or N02 and Rb is H, F or Cl-C2 alkyl with 0- 5F and Rc is CH3 or CF3; 15. R1 is H, Cl, Br, F, C,_C3 alkyl, N02, OCH3, 0 11 q_RdI CH20Rd, CF3, N=C=Q N(CH3)21 CN, S(O),,CH3 or CH2SW),,Cl-13 where n is 0 or 2; is H, Cl, F, Br, CH3 or OCH3; is 0 or S; is C,-C, alkyl, C,--C, alkenyl, C3--C., cycloalkyl, Cg-C, cycloalkenyl, C4-C7 cycloalkylalkyl, C3-C, cycloalkyl substituted with 1-2 CH3 groups, C,-C, alkynyf, CF2CF2H, CF2CHM, CF2CHffir, CF2CHCF3, C(CHICN, (CH2),,CN, where m is 1 or 2, CH, CH20CH3, CH2CH(CHACH3, (CHACH3, CHR7CO2R, or CHR7CON(J31)2, where R7 is H or CH3 and R,'S Cl-C3 alkyl, OCH3, R,' 20 W R2 CHR 7-Q or OCHR 7 25 119 9 R 9 where R9 is H, CH3, Cl, Br or F; R3 'S C,_C4 alkyl, C3__C4 alkenyl, CH2CH2OCH3, CH2CH(CHNOCH3, CH2CF, or (CH2).CN, where m is 1 or 2 or CHR7CO2R. or NR2R3 taken together are -N3 -N 0 or 30 provided that:

1) when R2'S OCH3, R3 is CH3; 2) when R2 is CF2CHM, CF2CHffir, CF2CF2H or CF.CHFU3, then R3!S C,_C4 alkyl; 3) when R, is M or N=C=Q it cannot be in the 3-position.

Preferred intermediates for reasons of higher activity and/or lower cost of derived herbicides of 35 Formula 1 are:

1) Compounds of Formula 1-B in which W 0.

2) Compounds of preference (1) in which R' H.

3) Compounds of preference (2) wherein A is OCH2CF3 or NR2R3 and R2S C, _C6 alkyl, C3-C4 alkenyl, OCH3, CH2CH2OCH3, CH2CH(CHJOCH3 or (CH2)30CH3, or NR2R3 taken together are 40 6 GB 2 057 429 A 6 -C, -143 r -N 0 or -0 \--i 4) Compounds of preference (3), wherein R3 'S Cl-C4 alkyl or where NR,R, taken together are -NC] -N 0 f k---/ or -N OCH 3 CH, 5) Compounds of preference (4), wherein R1 is H, Cl, CF3, N02, CH3 or OCH3.

6) Compounds of preference (5), wherein R-2 'S Cl-C4 akyl or NR2R3 taken together are - N - No Specifically preferred intermediates for reasons of highest activity and/or lowest cost of desired herbicides of Formula 1 are: N,N-Dimethyi-2- (isocyanatosuffonyl)benzenesuifonamide.

N-Ethyi-2-(isocyanatosuifonyi)-N-methyibenzenesuifonamide. 2(isocyanatosuifonyi)-N-methy]-N-(methylethyl)benzenesuifonamide. N,NDimethyl-2-(isocyanatosulfonyi)-4-trifl uorom ethyl benze nesulfon a mide. 2-[(2,2,2-Trifluoroethyi)suifonyllbenzenesuifonyl isocyanate.

Synthesis Many of the compounds of Formula 1 may be prepared as shown in Equation 4 by the reaction of 15 an appropriately substituted benzenesulfonyl isocyanate or isothlocyanate with an appropriate aminopyrimidine or aminotriazine. The benzenesulfonyl isocyanate and isothiocyanates are therefore important intermediates for the preparation of the compounds of this invention. The synthesis of these compounds is described in Equations 1-4.

Equation 1 so 2-A Ri 3 so 2 NE 2 R 1 II wherein A is NR2R3, OCH2CC13, OCH2CBr, OCH2CF2Rb or so 2 -A:

DABCO + COC1!!-c 4H 9NCO 6 1 1 2so 211,11C0 l- 4 ' Xylene/ 5 3 9.

Ref lux Ctr Ri R 2 0 Ra OCHRr 1 ';1-3 Ila where R is H, Cl, CH and R is H, F or Cl-C2 alkyl with 0-517 and R.

9 31 OCH3 or N02 b is CH3 or CF3.

R1 is H, Cl, Br, F, N02, Cl-C3 alky], OCH3, CF3, 0 11 k'hd or CH20Rd where Rd 'S Cl-C3 alkyl, N(CHI, CN, (0) 11 n CH 3 S-CH2 or CH3 S (0) 11 n c 41 7 GB 2 057 429 A 7 where n is 0 or 2; R,' is H, Cl, F, Br, CH. or OCH.; R2 is Cl-C, alkyl, Cl-C4 alkenyl, C:--C, cycloalkyl, Cg-C, cycloalkeny], C4-C, cycloalkylalkyl, C3-C, cycloalkyl substituted with 1-2 CH3 groups, C3-Cr, alkynyi, C(CHICN, (CH2).CN, where m is 1 or 2, CF2CF2H, CF2CHM, CF2CHFI3r, CF2CHFU3, CH2CF3, CH2CH2OCH31 CH2CH(CHACH31 5 (CH2)30CH3, or OCH., provided that when R2 is OCH3, R3 is CH3, CHM7K02R. or CH(R7)CON(R.)2, where Fl., is H or CH3, and R. is C,-C, alkyl; or R2'S CH (R7) 1 or OCHF 7 R 9 where R9 is H, CH3, Cl, Br or F; R3 is Cl-C4 alkyl, C3-C4 alkenyl, CH2CH2OCH3, CH2CH(CHACH3, (CH2)MM, where m is 1 or 2, CH(RX02%, -CH2CF3, or NR2R3 taken together are -C ' _N3 f -N 0 or - 11 0 provided that when R2 is CF2CHM, CF2CHFI3r, CF2CF2H, or CF2CHFCF3, then R3S Cl-C4 alkyl; Also provided that when IR, is M or N=C=Q it cannot be in the 3-poisition.

The above reaction is carried out by heating a mixture of the appropriate sulfonamide (11), an alkyl isocyanate such as butyl isocyanate and a catalytic amount of a tertiary amine such as 1,4 diaza[2,2,2]bicyclooctane (DABCO) in xylene, or other inert solvent of boiling point A 351 to approximately 1351. Phosgene is then added to the mixture over a 1-6 hour period until an excess of phosgene is present as indicated by a drop in the boiling point to less than 1301. The mixture is cooled 20 and filtered to remove a small amount of insoluble by-products. The solvent and the alkyl isocya-nate are distilled off M-vacuo leaving a residue of the crude, sulfonyl isocyanate, lla, which can be used without further purification.

The preparation of the suifonamides, 11, is described in Equation 8.

The sulfonyl isocyanates, lla, can also be prepared, as shown in Equation 2, by first preparing the 25 n-butyisuffonylureas 111; and, reacting the compounds Ill with phosgene.

Equation-2 n-c 4 H 9 NCO X2 C03 /Acet COC1 2 /DABCO iii Xylene/Reflux S02-A 0 11 wS02 NHCNHRC4H9 ill R! R 1 IIa wherein A, RI, R' R2 and R3 are as defined in Equation 1.

The compounds Ill are conveniently prepared by stirring a mixture of the sulfonamides, 11, 30 anhydrous potassium carbonate, and n-butyl isocyanate in acetone or methyl ethyl ketone at 25-800 until all of the isocyanate has reacted. The products are isolated by quenching in dilute mineral acid or by distilling off the solvent and recrystallizing the residue. The compounds Ill are treated with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in a manner analogous to that described in Equation 1.

Where W = S in Formula 1, the useful isothiocyanate intermediates, IV, are prepared according to Equation 3.

35.

8 - - GB 2 057 429 A 8 Equation 3 so 2-A so 2 NH 2 so 2 -A SK so 2 N==C SK SOrA 9 502 N=C-S RI R 1 iv wherein A R,, R', R2 and R3 are as defined in Equation 1.

+ CS 2 + KOH DMF -7 1 COC1 2 + XCI W.D The substituted sulfonamide is dissolved in dimethyiformamide (DMF) with an equivalent amount of carbon disulfide, and two equivalents of potassium hydroxide are added in portions-at room temperature. The mixture is stirred for 1-8 hours then diluted with ethyl acetate, ethyl ether, or other similar aprotic solvent to precipitate the dipotassium salt of the dithiocarbamic acid. The salt is isolated 10 and suspended in an inert solvent such as xylene, chloroform, or carbon tetrachloride. Phosgene is added below room temperature and the mixture stirred at room temperature for 1-3 hours. The sulfonylisothiocyanate is isolated by filtering off the precipitated potassium chloride and concentrating the filtrate. These compounds tend to dimerize on standing and therefore should be used soon after preparation.

Compounds of Formula 1 can be prepared by the reaction described in Equation 4.

Equation 4 so 2-A so 2 N-C=W +14 g- R i -R 6 Ri R 1 5 v wherein A, IR, % R2 and R3 are as defined in Equation 1; W is oxygen or sulfur; R5 is H or methyl; Re is 1 A 15.

so 2-A W 502-C-N-R 6 k H Ri R 1 1 N -< _ 0 z N -1 X Y 0 N -\/ - UO X Y1 0 or N - N --. p N -- X 1 1 9 xl 10 Y1 z GB 2 057 429 A 9 and X is H, CH3, CH30 or CH3CH20; Y is Cl, Br, H, C,_C3 alkyl, CF3, NHCH3, N(CH3)2, OCH2CF3, OCH3, OCH2CH3, SCH3, CH,M, NCH2M, 1 l^ CH2CH2M, CH2C1, N3, OCH,CH=CH2, OCH2C=_CH or O(CH2),OR10, where P is 2 or 3 and R10 is CH3 or CH3CH2, or Y is CH2CH2OCH3, CH20CH3, OCH(RX021111 or OCH(RACON(RJ2, CO2R,l and CH2C021111, R7 and R, are as previously defined; and R,, is H or Cl-C3 alkyl; is H, OCH3 or CH3; is H, OCH3, OCH2CH3 or CH3, provided that X, and Y1 are not both H simultaneously; and 10 is N or CH. The reaction of Equation 4 is best carried out in inert aprotic solvent such as methylene chloride, tetrahydrofuran, acetonitrile at a temperature between 20 and 800. A catalytic amount of DABCO may be used to accelerate the reaction. In the cases in which the products are insoluble in the reaction solven.

they may be isolated by simple filtration. When the products are soluble in the reaction solvent they are 15 isolated by evaporation of the solvent and trituration of the residue with solvents such as 1 chlorobutane ethylether, or methanol and filtration. Compounds of Formula 1 in which W = S and R5 = H can also be prepared by the reaction shown in Equation 5.

Equation 5 -A so 2 -A so 2-H + R' R 4 it R 1 SW-R 6 R' V1 R Ia 1 wherein is H or CH A, R$, R11 R2, R3 and R. are as defined in Equations 1-4, and R4 3.

2 so ' MR 2,11- 6 20 R 4' The reaction of Equation 5 is best carried out by suspending the suffonamide, the isothiocyanate and an equivalent of a base such as anhydrous potassium carbonate in a solvent such as acetone, methyl ethyl ketone, acetonitrile or ethyl acetate. The reaction is stirred at 25-80' for 1 to 24 hours. In 25 some cases, the product precipitates from the reaction mixture and can be filtered off, suspended in dilute mineral acid, filtered again and washed with cold water. If the product does not precipitate, it can be isolated by evaporation of the solvent, trituration of the residue with dilute mineral acid and filtering off the insoluble product.

The heterocyclic isothiocyanates, VI, which are used in the procedure of Equation 5 are prepared 30 according to the method of Japan Patent Application Pub. Kokai 51-143686, June 5, 1976; or that of W. Abraham and G. Barnikow, Tetrahedron 29, 691-7 (1973) both of which are herein incorporated by reference.

Compounds of Formula 1 in which W = S and R4 = H can also be prepared by the procedure shown in Equation 6.

Equation 6 so 2 -A so 2N=C=S 1) NaN-R R1 -0 - AS 2) H 3 0 1V so 2 -A S 11 02 NHCN-R 6 -71R1 R 1 1b wherein A, R', R,-R, are as defined in Equations 1-5.

In the procedure of Equation 6, the aminotriazine or aminopyrimidine is added to a suspension of sodium hydride in dimethylformamide (DIVIF) ortetrahydrofuran (THF) and allowed to stir at room 40 GB 2 057 429 A 10 temperature for 1-4 hours. The resulting salt solution or suspension is then added to a solution of the sulfonyl isothiocyanate in DMF or THF and allowed to stir at room temperature for 1-4 hours. The product is isolated by quenching the reaction mixture in excess dilute mineral acid and filtering off the insoluble product; or by first evaporating the solvent off and triturating the residue in dilute mineral acid 5 and collecting the solid product.

Alternatively, compounds of Formula 1 in which R4 is a methyl group may be prepared by the procedure shown in Equation 7.

Equation 7 so 2 -A W U so 2-C-Cl vii CH3 so 2 -A so -C-N-R6 2 1 R1 CH3 H R Ic wherein A, R', R,-R, and W are as defined in Equations 1-6.

H 2 N-R 6 31a Et 3 N The reaction of Equation 7 can best be carried out by adding an equivalent of an acid acceptor, such as triethylamine, pyridine, or potassium carbonate, to a mixture of the chloride VII, and the aminoheterocyclic, Va, in an inert organic solvent such as tetra hydrofura n, methylene chloride or 15 acetonitrile. Temperatures of 20-801 may beemployed. Soluble products can be isolated by filtering off the precipitated salts and concentration of the filtrate. Insoluble products can be filtered off and washed free of salts with water.

The chlorides of Formula VIl can be prepared by phosgenation or thiophosgenation of the N- methyisuifonam ' ide salts. The sulfonamide salt is added to an excess of phosgene-orthiophosgene in an 20 inert organic solvent, such as tetrahydrofuran or methylene chloride. After removal of the excess phosgene, the chloride VII can be isolated or reacted in-situ with the aminoheterocygle Va.

2-Aminopyrimidines are described by D. J. Brown in---ThePyrimidines-, Vol. M of---The Chemistry of Heterocyclic Compounds", Interscience, New York, and London. The 2-amino-1,3,5- triazines are reviewed by K. R. Huflman, in "The Triazines- of this same series. The synthesis of triazines is also described in U.S. Patent 3,154, 547, and by H. R. Huffman and F. C. Schaeffer,- J. Org. Chem. 28, 1816- 1821 (1963). All of the above are herein incorporated by reference.

The benzenesu Ifon am ides of Formula 11; which are the starting materials in Equations 1, 2 and 3, can be prepared by the four step procedure described in Equation 8.

so 2 cl 2 (8a) pi vill Al Z Equation 8 A-H VIIIa so 2 -A t 0 2 1 R 1 1X j 11 GB 2 057 429 A 11 Equation 8 -continued (8b) IX H 2 Pd/C S02-A k, NH 2 pi 1 X so 2-A (8c) X 1) HN02 /HCl so 2C1 2) SO 2 ICH 3 C02H/C2 /Or Ri xl R 1 (8d) wherein A, R,, R, R2, and R3 are as defined in Equations 1-7, with the exception that R, cannot be N02.

In step 8a, the o-nitrobenzenesuifonyl chloride in Formula VIII, which are well-known in the art, are treated with an amine or an alcohol of Formula Villa in an inert organic solvent such as methylene chloride, ethyl ether, or tetrahydrofuran at 0-50'. When Villa is an amine, it may be taken in excess to act as an acid acceptor; or, alternatively, a tertiary amine such as triethylamine or pyrimidine may be 10 used as an acid acceptor. When Villa is an alcohol, a tertiary amine such as triethylamine or pyridine must be used as an acid acceptor. The by-product amine hydrochloride is filtered off or washed out of the solvent with water and the product isolated by evaporation of the solvent.

The reduction described in step 8b is accomplished by treating a solution of the compounds of Formula]X, in a solvent such as ethanol, ethyl acetate, or DMF, in a pressure vessel, with 100-1000 15 pounds per square inch of hydrogen at 80-1501 in the presence of a hydrogenation catalyst such as 5-10% palladium absorbed on carbon. When the theoretical amount of hydrogen has been absorbed, the solution is cooled and the catalyst is removed by filtration. The product is then isolated by evaporation of the solvent.

In the case where R1 = N02, the reduction of step 8b can be accomplished using ammonium 20 suifide or sodium hydrosuifide instead of catalytic hydrogenation. This type of procedure is described in Organic Synthesis Coil. Vol. Ill, pgs. 242-3, John Wiley and Sons, Inc., New York and London (1955), the disclosure of which is herein incorporated by reference.

The diazotization and coupling with sulfur dioxide, described in step 8c, is accomplished in the following manner. A solution of the aniline of Formula X in a mixture of concentrated hydrochloric acid 25 and glacial acetic acid is treated with a solution of sodium nitrite in water at -5 to 01. After stirring for 10- 15 minutes at 00 to insure complete diazotization, this solution is added to a mixture of an excess of sulfur dioxide, and a catalytic amount of cuprous chloride in glacial acetic acid at 0-50. The temperature is kept at 0-51 for 1/4 to 1 hour then raised to 20-251 and held at that temperature for 2-4 hours. This solution is then poured into a large excess of ice water. The sulfonyl chloride products, 30 Xl, can be isolated by filtration or by extraction into a solvent such as ethyl ether or methylene chloride followed by evaporation of the solvent.

The amination described in step 8d is conveniently carried out by treating a solution of the suffonyl chloride of Formula XI with an excess of anhydrous ammonia in a solvent such as ethyl ether or methylene chloride at 0-251. If the product suifonamide, 11, is insoluble it may be isolated by filtration 35.

followed by washing out the salts with water. If the product sulfonamide is soluble in the reaction solution, it may be isolated by filtering off the precipitated ammonium chloride and evaporation of the solvent.

Compounds of Formula 1 in which R, = NH, can be prepared by the reaction shown in Equation 9.

NH 3 so 2-A /9 so 2 NH 2 Ri "I II 12 GB 2 057 429 A 12 Equation 9 S02 -A H 2 /pd-C - so 2-A Ri W pi (SO.1 -N-R6 -f -C so C-N-R 2 2','- 1 6 H2 N R R5 02N R 4 R 5 4 XII wherein A, R', RI-Ft. and W are as defined in Equations 1-8.

if The reduction described in Equation 9 is accomplished by treating a solution of the compounds of Formula XII in a solvent such as ethyl acetate or DMF in a pressure vessel, with 100-1000 pounds per square inch of hydrogen at 80-1500 in the presence of a suitable hydrogenation catalyst such as 5-10% palladium absorbed on carbon. When the theoretical amount of hydrogen has been absorbed, the solution is cooled and the catalyst is removed by filtration. The product is then isolated by evaporation of the solvent.

Compounds of Formula 1 can also be prepared by the method described in Equation 10.

Equation 10 S02 so 2 NH2 10a) Ri -0 R 1 X 2 N _ + O=C=N - 0 Z II so 2 A X RI -0 R 1 X 2 SO A 0 N 2 so 2 NHCIJH- 0 z p N - lob) i r Y R 1 XIV so 2 A 0 14 so 2 NWNH 0 Z Ri N _ Y 1 xv so 2A 0 OR12 19 S02N1ICNF- 0 Z 10c) P -t N _ R, Xlil Y 2 0 N - 2 it 1 S02NHCNH-- 0 Z N - XIV OR 12 Y 3 Xva 2 1 13 GB 2 057 429 A 13 Equation 10 -continued so 2 A 0 N _ OR 12 so 2 IMM 0 Z N - -0OR 13 R 1 so 2 A 10d) Ri 70 R 1 XIVa XV1 0 N M 0 z so 2 NHCIIH-- X 2 Y 4 so 2A 0 so 2 NHCNII-- 0 Z N - E R 1 wherein A, R,, and % are as described in Equation 1; R12 is methyl, ethyl, or -CH2CO2CH3; R13 is methyl or ethyl; 10 X2 is Cl or Br; Y2 is H, Cl, Br, methyl, ethyl or CF3; Y3 is Cl or Br; Y4 is methyl, ethyl or CF3; and E is (CHIN- or CHA' 15 Y XX CH3 1 -CMUU2UP13 6 Reaction Step (10a) In Reaction Step (1 Oa), an aromatic sulfonamide of Formula 11 is contacted with a heterocyc)ic isocyanate of Formula XIII to yield an N-(haloheterocyclicaminocarbony)) aromatic sulfonamide of Formula XIV.

The heterocyclic isocyanates used in Reaction (1 Oa) may be prepared according to methods 20 described in Swiss Patent 579,062, U.S. Patent 3,919,228, U.S. Patent 3, 732,223 and Angew Chern.

Int. Ed. 10, 402 (1976), the disclosures of which are herein incorporated by reference.

The aromatic sulfonamide and the heterocyclic isocyanate are contacted in the presence of an inert organic solvent, for example, acetonitrile, tetrahydrofuran (THF), toluene, acetone or butanone.

Optionally, a catalyticamount of a base, such as 1,4-diazabicyclo [2,2, 2]octane (DABCO), potassium 25 carbonate, sodium hydride or potassium tert-butoxide, may be added to the reaction mixture. The quantity of base constituting a catalytic amount would be obvious to one skilled in the art. The reaction mixture is preferably maintained at a temperature of about 25 to 11 WIC, and the product can generally be recovered by cooling and filtering the reaction mixture. For reasons of efficiency and economy, the preferred solvents are acetonitrile and THF, and the preferred temperature range is about 60to 85c1C. 30 Reaction Steps (1 Ob) and (1 0c) In Reaction Steps (1 Ob) and (1 Oc), one or two of the halogen atoms on the heterocyclic ring of the compound of Formula XIV is displaced by a nucleophilic species. Generally, this may be done by contacting thecompound of Formula XIV either with alkanol, R,,OH, or with alkoxide, -OR, 2, where RU is as defined above.

14 GB 2 057 429 A 14 Thus, in Reaction Step (1 Ob), a compound of Formula XIV, substituted with one displaceable group, can be contacted with at least one equivalent of alkanoi R OH This reaction is sluggish however alkoxide, (a) is 1 12. 1 and it is preferred to contact the compound of Formula XIV with at least two equivalents of -OR12. The alkoxide can be provided in a number of ways:

The compound of Formula XIV can be suspended or dissolved in an alkanol solvent, R120H, in the presence of at least two equivalents of alkaxide, -01112. The alkoxide can be added directly as alkali metal or alkaline earth metal alkoxide or can be generated by the addition to the alkanol solvent of at least two equivalents of a base capable of generating alkoxide from the solvent. Suitable bases include, but are not limited to, the alkali and alkaline earth metals, their hydrides and tert-butoxides. For example, when R12'S methyl, the compound of Formula 10 XIV could be suspended or dissolved in methanol in the presence of two equivalents of sodium methoxide. Alternatively, two equivalents of sodium hydride could be used in place of the sodium methoxide.

(b) The compound of Formula XIV can be suspended or dissolved in an inert solvent in the presence of at least two equivalents of alkoxide, -OR,,. Suitable inert solvents include, but are not limited to, acetonitrile, THF and dimethylformamide. The alkaxide may be added directly as alkali metal or alkaline earth metal alkoxide or may be generated from alkanol and a base as described in (a) above. For example, when R12'S methyl, the compound of Formula XIV could be suspended or dissolved in THF in the presence of two equivalents of sodium methoxide. Alternatively, two equivalents each of methanol and sodium hydride could be used 20 instead of sodium methoxide.

For reasons of economy and efficiency, procedure (a) is the more preferred method.

It should be noted that two equivalents of alkoxide are required for Reaction Step (1 Ob) whereas only one equivalent of alkanol is needed for the same process. This difference is due to the reaction which is believed to occur between the alkoxide and the sulfonyl nitrogen of the sulfonamide of Formula 25 XIV. When alkoxide is used, the first equivalent of alkoxide removes a proton from the sulfonyl nitrogen, and it is only the second equivalent which effects displacement of the halogen. As a result, two equivalents of alkoxide are required. The resulting salt must be acidified, e.g., with sulfuric, hydrochloric or acetic acid, to yield a compound of Formula XV. Applicant, of course, does not intend to be bound by the mechanism described above.

In Reaction Step (1 Oc) a compound of Formula XVa, substituted with at least one displacement group, is contacted with either one equivalent of alkanol, R130H, or with two equivalents of alkoxide, ---OR13 where R13 is as described above. The compound of Formula XVa is prepared according to Reaction Step (1 Ob) from a compound of Formula XV where Y2'S Cl or Br. When alkoxide, -OR13 is used, it may be provided in either of the methods described above in connection with Reaction Step 35 (1 Ob), and the resulting salt can be acidified to yield a compound of Formula XVI.

When R12 = R13, Reaction Steps (1 Ob) and (1 Oc) may be combined. Thus, a compound of Formula XIV may be contacted either with at least two equivalents of alkanol, R130H, or with at least three equivalents of alkoxide, -OR13.

When a compound of Formula XIV contains two displaceable groups, i.e., both X, and Y, are Cl 40 or Br, certain reaction conditions will favour displacement of only one of the group. These conditions are the use of low temperatures and, when alkaxide is used, the slow addition of the stoichiometric amount of alkoxide or alkoxide-generating base to the medium containing the compound of Formula XIV.

When alkoxide is used, both Reaction Steps (1 Ob) and (1 Oc) are preferably run at temperatures within the range of about -100 to 801C, the range of about 01 to 251C being more preferred. Reaction Steps (1 Ob) and (1 Oc) are more sluggish when alkanol is used instead of alkoxide, and more drastic conditions are required for the reaction to go to completion. Thus, higher temperatures, up to and including the boiling point of the alkanol itself, are required.

Reaction Step (10d) Reaction Step (1 Od) involves the displacement of the halogen atom in a compound of Formula XIVa by dimethylamino or methylthio nucleophiles. The starting material, a compound of Formula XIVa, is prepared according to Reaction Step (1 Oa), and Y4 is limited to Cl-C, alkyl and CF3.

For this reaction, the compound of Formula XIVa is suspended or dissolved in an inert solvent, such as acetonitrile or THE At least one equivalent of the nucleophilic species and at least two equivalents of a base are then contacted with the starting material. The first equivalent of base is believed to neutralize the sulfonamido proton. The second equivalent of base generates mercaptide or -N(CH,), from the mercaptan or the dialkylamine. Suitable bases include sodium hydride, sodium methoxide and sodium hydroxide.

Suitable reaction temperatures are within thd range of about -100 to 8WC, with a range of about 60 0' to 250C being preferred. The product may be isolated by dilution of the reaction mixture with water, mild acidification and filtration.

Compounds of Formula IX, which are intermediates in the preparation of the compounds of GB 2 057 429 A 15 Formula 11 - as described in Equation 8, can also be prepared by the procedures shown in Equations 11 and 12.

Eauation 11 NH 2 NO 2 11a) Ri -0 R 1 so 2 cl 1) IIINO2 /HCl Rit 0 2 -1 1 2) S02/CH3CO2H/CUC1 R 1 XVII so 2 cl 0 2 11b) Ri -01IN R 1 VIII wherein A, R, and R' are as described in Equation 1.

Vill so 2 A A-H Ri -t NO 2 R 1 IX The o-nitroanilines of Formula XVII are well known in the art. The method of converting compounds XVII to compounds V111 is analogous to that described in Equation (8c). The procedures for 10 converting compounds Vill to compounds IX are described in Equation. (8a).

Equation 12 B NO 2 12a) ' PC. r - R 1 XVIII -CH 2(D 12b) Ri -t NO 2 R1 xix so 2 cl NO 2 12c) 1 -0 R 1 wherein Vill A, RJ, R,' are as described in Equation 1; B is Cl or Br; and M is Na or K.

& CH 2 SH X MOH SCH 2 ( 1 NO 2 Ri-0 R 1 xix so 2 cl cl 2/CH3 CO 2 H V2 H 2 0 R 1 VIII so 2 A N02 Ri - r R 1 IX GB 2 057 429 A 16 In Step (1 2a), the compounds of Formula XVIII, which are well known in the art, are reacted with benzy] mercaptan in the presence of an equivalent amount of a base such as sodium or potassium hydroxide. The preferred solvent for this reaction is an alcohol such as methyl, ethyl or isopropyl alcohol. The reaction can be carried out at temperatures between 25 and 801 but temperatures of 50-800C are preferred. The products of Formula XIX are isolated by cooling the reaction mixture to 0-201, filtering off the precipitated product, and washing this solid with water to remove the by-product alkali halide.

In Step (1 2b), the compound of Formula XIX is suspended in a mixture of 85-95% acetic acid and 5-15% water. This suspension is treated with at least three molar equivalents of chlorine at 0-2011. When a clear solution is obtained, the reaction solution is quenched in an excess of ice water and extracted with a solvent such as methylene chloride, chloroform or 1 -chlorobutane. The products of Formula VIII are isolated by concentrating this solvent extract in vacuo to remove the solvent and the by-product benzyl chloride. The products are oils or low melting solids and may be used directly in the next step or recrystallized first from such solvents as cyclohexane or 1 - chlorobutane.

Compounds of Formula M, in which A includes certain fluoroalkylamine moieties can also be 15 prepared by the procedure shown in Equation 12a.

Equatio 12a NO 2 NO 2 so =C.,-F so 14-CF CH 2-H CF2 -,G 2 ' 2 3 Base/DMF 1) 3 Ri R R 1 IX wherein IXa R, and R' are as previously described; R, 'S Cl-C4 alkyl, and G is F, Cl, Br or CF, The reaction described in Equation 12a is accomplished by heating a mixture of the sulfonamide IX, one or two equivalents of the fluoroolefin and a catalytic amount of base in dimethyiformamide solution in a pressure vessel at a temperature of between 60 and 1301 until a pressure drop is no longer observed. Appropriate bases for this reaction include potassium hydroxide, sodium hydroxide, sodium 2-5 hydride and sodium metal. The products of the reaction are isolated by quenching the reaction mixture in a large excess of water and extraction with n-buty[ chloride or diethylester. Evaporation of the solvent yields the desired sulfonamides Ra as viscous oils.

Compounds of formula M in which A includes a benzyloxyamine group may also be prepared by the procedure described in Equation 12b.

Equation 12b 30 N02 Ri + -f;G so 2 c 1 R 1 Vill R 1 H 110CP 1 9 2 R 7 -Q R R1 NO 2 S02NHOC,H-(, R 7 R UC NO 2 3 N-OCH IX R so 29 1 R 3 R 7 R IM 17 GB 2 057 429 A 17 wherein RJ, R', R3, R7 and R. are as previously described.

In the first step of Equation 12b, a sulfonyl chloride of Formula X111 is reacted with an appropriate benzyloxyamine, taken in excess to act as an acid acceptor, in diethyl ether or tetrahydrofuran solution at 0-101. The reaction is completed by stirring at ambient temperature for 4-24 hours. The solvent is 5 evaporated and the product sulfonamide Wc purified by washing the residue with water to remove the by-product amine hydrochloride.

In the second step of Equation 12b, the sulfonamide of Formula Wc is stirred at ambient temperature for 18-24 hours with an excess of both an alkyl iodide and anhydrous potassium carbonate or sodium carbonate in acetone or 2-butanone solution. The solvent is evaporated and the 10 residue partitioned between methylene chloride and water. Concentration of the methylene chloride solution affords the compounds of Formula 1M as pale yellow oils.

The compounds of Formula 1M may be converted to compounds of Formula M by the procedure described in Equation 12c.

Rj Equation 12C NO 2 GSI02c)CH CH CO H P-3 R9 3 2 1M Re NH 2 CS02 OCH-& R R3 R 7 M wherein Fe R 9 R,, R', R3, R7 and R. are as previously described.

The conversion in Equation 12e is accomplished in the following manner: A solution of the nitro compound Rd is 90% aqueous acetic acid is treated with an excess of iron powder (5 g - atom/mole 20 of IM) at 80-901 in several portions. After heating an additional 20 minutes, charcoal is added and the solution filtered through Celites and concentrated in-vacuo. The residue is made strongly alkaline with 20% sodium hydroxide then extracted with methylene chloride. Concentration of the organic solution yields the anilines of Formula Xcl as viscous oils.

The compounds of Formula Xcl may be converted to the compounds of Formula 1 by the procedures described in Equations 1-8.

Compounds of Formula 1 in which R2 is hydrogen may be prepared by the procedure described in Equation 12d.

Equation 12d so 2,'-OC R R H-'k R! 3 W 7 9 f(SO C-N-R R 2','_ " 9 6 R 4 R 5 1h so 2 NHR 3 W so C-N-R 2-" 6 R 4 A 5 ii BEIr 3 18 GB 2 057 429 A 18 wherein R,, IR', Rg----R, and W are as described previously.

In the reaction of Equation 12d, an excess of boron tribromide is added to a suspension of the compound of Formula 1h in a solvent such as benzene, toluene or xylene at ambient temperature. The reaction may be completed by stirring at room temperature or it may be necessary to heat the reaction mixture up to 1381 for up to 24 hours. After completion, the reaction is quenched by the addition of water and the product tCiturated with hexane. The products of Formula 12i are solids and are isolated by filtration.

The conversion of compounds VIII to compounds K is described in Equation (8a).

Compounds of,Formula 1 in which R, is -N=C=Q 0 0 11 11 NtiCNHRd and Nrit'Urld can be prepared by the procedures described in Equation 13.

so 2 A 0 19 Equation 13 -13a) 0 2 N=HnC4 H 9COC12 R1 H i-ol NH 2 Ma so 2 A so 2 NCO 13b) -91H 1 OCN lib + HN-R 1 6 R 5 v so 2 A 0 %1 SO NWN-R 13c) 2 1 6 Ri R 5 OCN ld wherein so 2A 101 S02MC-N-R6 R! -k, i 5 0 t, le H-C-T-Rd So 2 A so 2 NCO i-Q H OW H-T-Rd ------ xxi lib S02A 0 11 0 NHC14-R 2 6 pi H OW id A, R', R. and R. are as previously described; Rd is C,-C3 alkyl; and T is 0 or NH.

In Step (1 3a), the compounds of Formula Ilia, which are well known in the art, are added to at 20 least two equivalents of phosgene in an inert solvent such as xylene or chlorobenzene at 0-51. A slow stream of phosgene is then introduced and the reaction temperature raised to 1300 (reflux). Refluxing the reaction mixture for 1-2 hours, followed by purgation with nitrogen, filtration, and concentration yields the products of Formula lib, as viscous oils. These compounds may be further purified by vacuum distillation.

In Step (1 3b), the compounds of Formula lib are reacted with the aminoheterocycles of Formula V in an inert solvent such as methylene chloride, acetonitrile, or tetrahydrofuran at 20-501 over a period of two to twenty-four hours. A catalyst, such as DABCO, may be used to accelerate the reaction. The products are isolated by removing the solvent via concentration in vacuo.

19 GB 2 057 429 A 19 In Step (1 3c) the compounds of Formula ld are reacted with amines or alcohols of Formula XXl in an inert solvent such as methylene chloride, chloroform, acetonitrile or tetrahydrofuran at 20-800 over a period of two to twenty-four hours. The reaction may be accelerated by addition of a catalyst, such as DABCO, and by the use of two equivalents of the a mine, XXI. The products, le, are isolated by removing 5 the solvent via concentration in vacuo.

Compounds of Formula 1 in which R, is 11 "Jrlk'rld 0 can be prepared by the reaction described in Equation 14.

Equation 14 so 2A for so 2 NWN-R 6 R! -0 A 5 H 2 N 0 19 R dC-Cl so 2 A 0 Re SO NHCN-R 2 # 6 M1 RdCHN if 1g wherein A, %, Rd, R5 and R, are as previously described.

In the procedure described in Equation 14, the compounds of Formula If are reacted ith an acid chloride of Formula-XXII in an inert solvent such as chloroform, methylene chloride or tetrahydrofuran at ambient temperature in the presence of an acid acceptor such as pyridine or triethylamine. The reaction takes four to twenty-four hours for completion. Both the acid chloride, XXII, and the acid acceptor may 15 be taken in excess to hasten the completion of the reaction. The products, lg, are isolated by filtering- off the by-product amine hydrochloride and concentrating the filtrate in vacuo. The crude products thus obtained may be purified by recrystallization or by column chromatography.

The compounds of Formula IA can be prepared from the compounds of formula 1 in which W is sulfur by the process described in Equation 15.

Equation 15 2 A S N - X N-C:NH- OZ S02 A N:( (15a) R 1 Ij Y 1 SO 2 A Q S-M N-l R so 2 N= -NH - C) z N - I k Y so 2 A S-B N R 9S02N= -NH- C) Z 1 N (15b) ik IA Y 1 A, RJ, X,, Y, and Z are as described previously and B is C,-C,, alkyl; CH2CH2OCH; CH,CH20CH2CH,; CH2CH2CH2OCH3; CHA; wherein GB 2 057 429 A 20 CH-G; 1 Lth where G is C0i-IC1-, alkyl, 0 CH3 0 11 / 11 -UN OCH3 0 11 -t"Mkk-1-3 kllkyl)21 -CNI-I(C1-C3 alkyO, 1 1 1 phenyl, phenyl substituted with chlorine, CN, C2-4 alkenyl, C2-, alkynyl, --OR',, where R', is C -C4 alkyl, -CH20CH2CH2OCI-13 or -CH20CH2CH2OCH2CH3 and M is an alkali or alkaline earth metal.

In step (1 5a) the thiourea of Formula lj is treated with an alkali or alkaline earth alkoxide, hydride, hydroxide or carbonate in tetrahydrofuran or diethyl ether suspension to obtain the salt lk at ambient temperature up to 62. In step (1 5b) the salt suspension as solution is treated with the appropriately substituted iodide or bromide at 35 to 621 for 1-4 hours. The reaction mixture is then cooled to ambient temperature. If the product is insoluble, it may be isolated by filtration from the reaction mixture. If the product is soluble in the reaction solvent, it may be isolated by the reaction solvent, it may be isolated by evaporating the solvent and triturating the residue with a solvent such as cyclohexane or 1 - ch - lorobutane. The product la may be purified by recrystallization from a suitable solvent such as acetonitrile.

Agriculturally suitable salts of compounds of Formula 1 and Formula IA are also useful herbicides 15 and can be prepared in a number of ways known to the art. For example, metal salts can be made by treating compounds of Formula 1 with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g. hydroxide, alkoxide, carbonate or hydride) quaternary amine salts can be made by similar techniques. Detailed examples of such techniques are given in United States Patent 4,127,405, the disclosure of which is herein incorporated by reference.

The compound of this invention and their preparation are further illustrated by the following examples wherein temperatures are given in degrees centigrade and all parts are by weight unless otherwise indicated.

EXAMPLE 1 o-Nitro-N,N-diethyibenzenesuifonamide To a solution of 132.6 of o-nitrobenzenesuifonyl chloride in 700 mi of tetrahydrofuran was added 88.5 9 of diethylamine at 5-151. The reaction mixture was stirred at room temperature for 1 hour before the precipitated diethylamine hydrochloride was removed by filtration. The filtrate was evaporated to dryness in-vacuo and the residue dissolved in 1 - chlorobutane. The 1 -chlorobutane solution was washed with water, dried over magnesium sulfate and evaporated in-vacuo to give 122.4 30 g of o-nitro-N,N-diethylbenzenesuifonamide as a dark oil.

NIVIR(CWO:

1. 1 -1.4 [t, 6.1 H, (CH.CH2)2N-I; 33-3.8 [qt, 3.81-1, (CR3CH2)2N-I; 8.0-8.6 (m, 4.1 H, 4 aromitics).

EXAMPLE 2 o-Amino-N,N-diethyibenzenesuifonamide In a pressure vessel a mixture of 133 g of o-nitro-N,N- diethylbenzenesuifonamide, 5 g of 10% palladium on carbon, and 500 mi of ethyl acetate was shaken at 1301 under 500 psi hydrogen pressure until hydrogen was no longer absorbed. The reaction mixture was cooled and the catalyst filtered off. 40 Evaporation of the solvent in-vacuo gave 123 g of o-amino-N,Ndiethyibenzenesuifonamide as a viscous oil which slowly crystallized to a solid, m.p. 45-51 NMR(CDCI,)8:

1.0-11.3 R, 6.7H, (CH,CH2)2N-I; 10-3.5 [qt, 3.61-1, (C93CH2),N-]; 4.8-5.2 (broad, 1.71-1, N1-1111 6.5-7.7 (m, 4.0H, 4 aromatics).

EXAMPLE 3

N,N-Diethyl-1,2-benzenedisuifonamide To a solution of 114 g of o-amino-N,N-diethyibenzenesuifonamide in a mixture of 400 mi of 50 concentrated hydrochloric acid and 100 mi of glacial acetic acid was added a solution of 50 9 of sodium nitrite in 130 mi of water at -5 to 01. The solution was stirred at 0' for 15 minutes then poured into a mixture of 14 9 of cuprous chloride and 100 mi of liquid sulfur dioxide in 550 mi of glacial acetic-acid at _t <1 21 GB 2 057 429 A 21 0-50. This mixture was stirred at 00 for 15 minutes then at room temperature for 3 hours before pouring into three liters of ice water. The crude sulfonyl chloride was filtered off and washed with water. It was then dissolved in 1 1 of ethyl ether, washed with water and dried over magnesium sulfate. To this ether solution was added 20 mi of liquid anhydrous ammonia at 5-15. After stirring overnight at room temperature the solid was filtered off, washed with water, ethanol and then 1 - chlorobutane. Oven 5 drying at 600 gave 91.8 g N,N-di ethyl- 1 2- benzenedisuifona mide, m.p. 156-91 NIVIR(DIVISOW 0.9-1.2 R, 6.0H, (CH,CH2)2N-j,. 3.2-3.6 [qt, 3.8H, (CR3CH2)2N-I;,7.2 (broad singlet, 2.1 H, 9H2); 73-8.4 (m, 4.1 H, 4 aromatics).

EXAMPLE 4 o-N,N-DiethyisulfamoylbenzenesuifonyI isocyanate A solution of 13.2 g of N,N-diethyi-1,2-benzenedisuffonamide, 4.5 g of nbutylisocyanate, and 0.2 g of 1,4-diaza[2,2,2]bicyclooctane (DASCO) in 90 mi of mixed xylenes was' heated to 1351. To this 15 solution was added 3.3 mi of liquid phosgene at such a rate that the temperature was maintained between 125 and 135 (about 2 hours). The temperature was kept at 1301' for 1/2 hour after the addition. The solution was cooled and filtered to remove a small amount of insoluble solid then concentrated at 60-7011 in-vacuo. The residue of o-N,N- diethyisulfamoylbenzenesuffonyI isocyanate was an oil weighing 16.8 g and was sufficiently pure for further reaction.

EXAMPLE 5 N,N-Diethyl-N'-[(4-methoxy-6-methylpyrimidin-2yl)aminocarbonyll-1,2-benzene disuifonamide A mixture of 0.8 g of 2-amino4-methoxy-6-methylpyrimidine, 2.8 g of the crude sulfonyl isocyanate from Example 4 and a few crystals of DABCO in 25 mil of acetonitrile was stirred at room temperature for 16 hours. A small amount of unreacted aminopyrimidine was filtered off and the filtrate 25 concentrated in-vacuo to give a hard glass. Crystallization from methanol gave 0.9 g of N,N-diethylN'[(4methoxy-6-methylpyrimidin-2-yl)aniinocarbonyi-1,2-benzenedi suifonamide as a 'white solid, m.p. 170-20.

Anal. Calcd. for C171-123N5O.S2: C, 44.62; H, 5.07; N, 15.31.

Found:

NIVIR(DIVISO-d,W 0.9-1.2 R, 6.0H, (CH,CH2)2N-I; 2.3 (S, 2.8H, Het -CWj; 3.1-3.5 [qt, 4.3H, (CH3CH2)2N-I; 3.9 (S, 3.0H, Het -OCH3).

6.5 (S, 0.9H, Het -H); 73-8.5 (m, 4.3H, 4 aromatics); 10.6 (S, 1.0H, NW; 13.4 (S, 0.8H, NW.

EXAMPLE 6

N,N-Diethyi-N'-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyll-1,2benzene disuifonamide A mixture of 0.9 9 of 2-amino-4,6-dimethoxy-1,3,5-triazine, 2.8 9 of the crude sulfonyl isocyanate from Example 4 and a few crystals of DABCO in 25 mi of acetonitrile was stirred at room temperature for 16 hours. A small amount of untreated triazine was filtered off and the filtrate concentrated in vacuo to a hard glass. Crystallization from methanol gave 0.6 g.of N,N-diethy]- N'[(4,6-dimethoxy-1,3,5-triazin2yi)aminocarbonyll-1,2-benzenesuifonamide as a white solid, m.p. 175-711 NIVIROMSO-d6W 0.91-1.2 R, 6.0H, (CH3CH2)2N-I; 3.1-3.5 [qt, 4.3H, (CR3CH2)2N-I; 3.95 (S, 5.5H, -OCH3'S); 7.9-8.5 (m, 4.1 H, 4 aromatics); 11.2 (S, 0.9H, NI-1); 12.4 (S, 1.1 H, NH).

C, 44.5, 44.4; H, 5.09, 5.09; N, 15.4, 15.5. 30 EXAMPLE 7 55 2-N itro- 1 -[(phenyl methyi)thiol-4-trifi uorom ethyl benzene To a mixture of 225.6 g of 4-chloro-3-nitrobenzotrifluoride and 136 g of benzy] mercaptan in 1.5 1 of ethyl alcohol, at reflux, was added a solution of 72.5 g of 85% KOH in 120 mi of water over a 45 22 GB 2 057 429 A 22 minute period. Reflux was continued for an additional three hours. The reaction mixture was cooled to 51C. The precipitate was filtered off, washed with ethanol and water and dried to give 273.2 9 of 2 nitro-1 -[(phenyl m ethyl)thiol-4-trifi u oro methyl benzene as a bright yellow solid, m.p. 132-1361.

NMR(DMSO-d6)8:

4.45 (s, 1.9H, SCH, 7.2-7.7 (m, 5.OFf5 aromatics); 7.9-8.2 (m, 2.1 H, 2 aromatics); 8.5 (s, 1.0H, 1 aromatic).

EXAMPLE 8

N,N-Dimethyi-2-nitro-4-(trifluoromethyi)benzenesuifonamide To a suspension of 156.5 g of 2 -n itro- 1 -[(phenyl methyi)thiol-4-trifi uorom ethyl benzene in a mixture of 800 mi of acetic acid and 100 mi of water was added 78 mi of liquid chlorine at 10-181 over a 1 hour period as the suspension gradually turned into a clear solution. The solution was stirred at 18-251 for 2 hours, then poured into 1 1 of ice water. The mixture was extracted with 1 -chlorobutane and the 1 -chlorobutane extract washed well with water. The solution was dried over M9SO, and stripped, finally at 70-801/1-2 mm, to give 164 g of crude sulfonyl chloride as a light yellow oil. This oil was dissolved in 600 mi of methylene chloride, cooled to 51, and treated with 75 mI of liquid dimethylamine at 5-151. After stirring at 251 for 1 hour, the reaction mixture was washed with water, dried over MgS04, and stripped in vacuo to give a crude solid. This solid was slurried in ethanol, filtered and washed with ethanol, and dried to give 109.1 g of N,N-di methyl-2 -n itro-4-(trifi uorom ethyl)benzenesuifonamide, m.p. 102-104.51.

NMR(DMSO-d,,)8:

2.9 (s, 6.1 H, NMe.); 8.3 (s, 2.0H, 2 aromatics); 8.7 (s, OSH, 1 aromatic).

Anal. Calcd. for C^F3N204S Found:

C, 36.25; H, 3.04; N, 9.39; S,10.75.

C, 3 6.4, 3.6 5; H, 3.00, 3.04; N, 9.58, 9.52; S, 11.1, 11.0.

EXAMPLE 9

2-Amino-N,N-dimethyf-4-(trifluoromethyf)benzenesuifonamide In a pressure vessel, 109 g of N,N-cl imethyi-2-n itro-4-(trifi uorom ethyl) benzenesu Ifona mide, 250 mi of ethyl acetate and 5 g of 10% palladium-on-carbon were shaken at 1301 under 500 psi hydrogen pressure until no more hydrogen was absorbed, as determined by no additional pressure drop. The reaction mixture was cooled and the catalyst filtered off. The solution was stripped in vacuo to give 95.2 g of 2-amino-N,N-dimethyl-4-(trifluoromethyi)benzenesuifonamide as a slowly crystallizing oil, rn.p. 35 65-700C.

NIVIR(WC1J8:

2.8 (s, 5.8H, NMe,); 5.1-5.6 (broad, 2.2H, NN; 6.9-7.9 (m, 3.0H, 3 aromatics).

EXAMPLE 10

N 1,N '-Dim ethyl-4-(trifl uoromethyi)- 1,2-benzenedisulfona mide To a suspension of 38.0 g, of 2-amino-N,N-dimethyi-4(trifluoromethyi)benzenesuifonamide in a mixture of 115 mi of concentrated hydrochloric acid and 40 mi of glacial acetic acid was added a solution of 14.0 g of sodium nitrite in 40 mi of water at -5 to 00 over a 30 minute period. The resulting 45 diazonium solution was stirred at 0' for 15 minutes. This diazonium solution was then added to a solution of 4.0 g of cuprous chloride and 26 mi of liquid sulfur dioxide in 175 mi of glacial acetic acid at 51 over a 10 minute period. The resulting mixture was stirred at 01 for 1 hour and at 251 for 2 hours before pouring into 1 1 of ice water. The precipitated sulfonyl chloride which formed was filtered off and washed well with water. The still-wet sulfonyl chloride was suspended in 350 m] of diethyl ether, cooled to 51 and treated with 7.0 mi of liquid ammonia. The reaction mixture was stirred at room temperature for 1 hour. The precipitate was filtered-off, washed with ether, water and then ethanol to give 22.4 g of N 1, W-di methyl-4-(trifi uorom ethyl)1,2- benze nedisu Ifona mide as a white solid, m.p. 189-1910.

NIVIR(DIVISO-drJS:

2.7 (s, 6.1 H, -NMe2); 7.3 (broad singlet, 1.9H, -S02NH2); 8.0-8.4 (m, 3.0H, 3 aromatics).

so GB 2 057 429 A 23 EXAMPLE 11 NI-(Butylaminocarbonyl)-N,N-dimethyi-4-(trifluoromethyi)-1,2benzenedisulfon amide A mixture of 49.7 g of NI, NI-d i m ethyl-4-(trifl uorom ethyl)- 1,2 - benzenedis ulfona mide 22.5 g of nbutylisocyanate, and 3 1.1 g of anhydrous potassium carbonate in 600 mi of 2-butanone was stirred at reflux for four hours. The mixture was cooled to 250 and poured into 1.6 1 of ice water. The solution was acidified to pH = 1 with concentrated hydrochloric acid. The precipitate was filtered off and washed with water and 1 -chlorobutane. Drying overnight at 601 in vacuo gave 55.6 g of W- (butyl a minoca rbonyl)-N, N-di m ethyl-4-(trifl uorom ethyl)- 1,2-benze nedisu Ifona mide as a white solid, m.p. 128-1301.

NIVIR(DIVISO-d')S:

0.8-1.6 (m, 7.7H, 7 butyl hydrogens); 2.8-3.5 (m, 7.5H, NMe2 + CH2NH); 6.8-7.1 (m, 0.9H, NHCH2); 8.4-8.8 (m, 3.1 H, 3 aromatics); 10.3 (broad, 0.9H, NH).

EXAMPLE 12 2-(N, N-Di methyisu Ifa moyi)- 5-(trifl uorom ethyl) be nzenesu Ifonyl isocya nate A solution of 12.5 9 of W-(butyl am inocarb -0 nyl)N,N-di methyl-4-(trifl uoromethyl)- 1 2 -benzenedisulfonamide, and 0. 1 g of DABCO in 75 mi of mixed xylenes was heated to 1361. To this solution was added 2.2 m] of liquid phosgene over a period of two hours at a rate that the temperature was maintained between 1250 and 1351. The temperature was kept at 1301 for 1/2 hour after the addition. The solution was cooled and filtered under a nitrogen atmosphere to remove a small amount of insoluble solid then concentrated at 60-700 in vacuo. The residue of 2-(N, N-dimethyisulfamoyl)-5(trifl u oro m ethyl)benzenesu Ifonyl isocyan ate was an oil weighing 10.4 9 and was sufficiently pure for further reaction.

NMR(DMSO-dr,)8:

2.9 (s, 3.8H, NMe2); 3.9 s, 6.1 H, Het-OCI-13'S); 6.0 (s, 1.2H, Het-H); 8.2-8.6 (m, 2.9H, 3 aromatics); 10.8 (broad, 1.0H, NI-1); 13 (broad, 1.0H, NW. EXAMPLE 14 2,2,2-Trifluoroethyl 2-nitrobenzenesulfonate To a solution of

110.5 g of o-nitrobenzenesuifonyl chloride and 50.0 g of 2,2,2-trifluoroethanol in 600 mi of diethyl ether was added 52.0 g of triethylamine at 5-151 over a 45 minute period. The reaction mixture was stirred at 251 for 1 hour then washed with water, dried over M9S04, and stripped in vacuo to give 2,2,2-trifluoroethyl 2-nitrobenzenesulfonate as an oil weighing 110.3 g. 50 NMR(CDCI,)&:

4.3-4.8 (qt. 1.8H, CH2CF.) 7.8-8.4 (m, 4.2H, 4 ai-romatics).

EXAMPLE 13 NI-[(4,6-Dimethoxypyrimidin-2-yi)aminocarbonyll-N',Nl-dimethyi4-(trifluarom ethyi)-1,2-benzenedisulfonamide A mixture of 2.6 g of crude 2-(N,N-dimethyisulfamoyi)-5- (trifluoromethyi)benzenesuifonyliso30 cyanate, 0.9 g of 2-amino-4,6- dimethoxypyrimidine and a few crystals of DABCO in 15 mi of acetonitrfle was stirred under a nitrogen atmosphere at 250 overnight. The precipitate was filtered off, washed with acetonitrile and dried to give 0.7 g of N2- [(4,6-di methoxypyri midi n-2-yl)a mi noca rbonyllN 1, N 1 -dim ethyl -4- (trifl uoro m ethyl) 1,2 -benze nedisu Ifona mide, m.p., 194-60 (d).

Anal. Caled. for C1.Hj3N.07S2: C, 37,43; H, 3.53; N, 13.64; F,11.10.

Found: C, 37.5, 37.6; H, 3.57, 3.65; N, 14.0, 14.0; 35 F, 11.47 EXAMPLE 15

2,2,2-Trifluoroethyl 2-aminobenzenesulfonate In a pressure vessel, 107 g of 2,2,2-trifluoroethyl 2- nitrobenzenesulfonate and 8 g of 5% 55 palladium-on-carbon in 300 mi of ethyl acetate was heated to 1101 and shaken under 500 psi hydrogen pressure until hydrogen was no longer absorbed. The reaction mixture was cooled and the catalyst filtered off. The filtrate was stripped in vacuo to give 87.5 g of 2,2,2-trifluoroethyl 2-amino- 24 GB 2 057 429 A 24 benzenesuffonate as a dark oil. NIVIR(WC13)8:

4.0-4.4 (qt. 2.0H, CH2CF3); 4.8-5.4 (broad, 1.9H-NH2); 6.5-7.8 (m, 4.1 H,' 4jaromatics).

EXAMPLE 16 2,2,2-Trifluoro 2-(aminosuifonyi)benzenesuifonate Using a procedure analogous to that described in Example 10, 63.8 g of the product of Example 15 was converted to 38.4 g of 2,2,2-trifluoro 2-(a minosulfonyl) benzenes u Ifonate, m.p. 97-1000 10 (recrystallized from 11chlorobutane). NMR(DMSO-de)S:

4.4-4.9 (qt. 1.9H, CH,CF3); 6.8-7.1 (broad singi6-t, 1.9H, S02NI-12); 73-8.6 (m, 4.2H, 4 aromatics).

EXAMPLE 17 (2,2,2-Trifluoroethyi) 2[[(butylamino)carbonyllaminosuifonyllbenzenesuifonate Using a procedure analogous to that described in Example 11, 35.1 g of the product of Example 16 was converted to 45.0 g of (2,2,2- trifluoroethyi) 2-[[butylamino)carbonyllaminosuifonylj benzenesulfonate, m.p. 140-2.50. 20 NIVIR(DIVISO-d')S:

0.7-1.4 (m, 7.2H, 7 butyl hydrogens); 2.7-3.2 (m, 2.1 H, 2 butyl hydrogens); 4 ' 6-5.1 (qt, 2.0H, CH2CF); 6.5-6.9 (broad t, 0.9H, NFICH2); 7.9-8.6 (m, 3.811, 4 atomatics).

EXAMPLE 18 2,2,2-Trifluoroethyl 2-(isocyanatosuifonyi)benzenesuifonate Using a procedure analogous to that described in Example 12, 20.6 g of the product of Example 17 was converted to 16.6 g 6f 2,2,2-trifluoroethyl 2-(isocyanatosuifonyi)benzenesuifonate, obtained as 30 a crude oil.

EXAMPLE 19 (2,2,2-Trifluoroethyi) 2-[[(4,6-di methoxypyri midin-2-yi)a minocarbonyll am inosu Ifonyll benzenesulfonate Using a procedure analogous to that described in Example 13, 2.7 g of the product of Example 18 was converted to 1.9 g of (2,2,2-trifluoroethyi) 2-[[4,6dimethoxypyrimidin-2yi)aminocarbonyllaminO- 35 suifonyllbenzenesuifonate, m.p. 203-50.

Anal. Calcd. for C,,H1,173NAS2 Found:

NIVIR(DIVISO-d6W C, 36.00; H, 3.02; N,11.20.

C, 36.1, 36.7; H, 2.96, 2.90; N, 11.2,11.3.

3.85 (s, 5.9H, Het-OCH3'S); 4.7-5.1 (qt, 2.2H, CH,CF3); 5.9 (s, 1.2H, HetH); 8.0-8.7 (m, 4.1 H, 4 aromatics); 10.7 (s, 0.9H, NH); - 13 (broad, 0.7 H, NW.

EXAMPLE 20

N,N-Dimethyi-4-methoxy-2-nitrobenzenesuifonamide A mixture of 84.0 g of 4-methoxy-2-nitroanifine, 400 mi of conc. hydrochloric acid, and 200 m] of acetic acid was treated with a solution of 50 g of sodium nitrite in 120 mi of water over a 45 minute period at -5 to 0'. The resulting solution was stirred at 01 for 15 minutes. This diazonium solution was 50 added to a solution of 12 g of cuprous chloride and 100 mi of sulfur dioxide in 600 mi of acetic acid over 15 minutes at 0-51. The mixture was stirred at 01 for 1 hour and at 251 for 2 hours before pouring into 4 1 of ice water. The precipitated sulfohyl chloride was filtered and washed well with water.

The still-wet sulfonyl chloride was suspended in 600 mi of diethyl ether, cooled to 01, and treated with 55 mi of liquid dimethyl amine at 0-101. After stirring at room temperature for 30 minutes, the precipitate was filtered and washed with ether, then water. Drying at 600 in vacuo gave 92.0 g of N,N dimethyi-4-methoxy-2-nitrobenzenesuifonamide as a white solid, m.p. 90- 92'.

GB 2 057 429 A 25 NMR(DMSO-d,)&:

2.7 (s, 6.1 H., -NMe,); 3.9 (s, 2.9H, OCH3); 7.2-8.0 (m, 2.9H, 3 aromatics).

EXAMPLE 21 N,N-Dimethy]-2-amino-4-methoxybenzene-suifonamide In a procedure analogous to that described in Example 9, 90.0 g of the product of Example 20 was converted to 66.4 9 of N,N-dimethyi-2-amino-4methoxybenzenesuffonamide, obtained as a dark, slowly crystallizing oil, m.p. 59-641.

NIVIR(CIDC10:

2.7 (s, 5.7 H, N M e2); 3.7 (s, 3.0H, OCH3); 4.9-5.3 (broad, 2.0H, NH2); 6.2-6.5 (m, 2.2H, 2 aromatics); 7.21-7.6 (m, 1.2H, 1 aromatic).

EXAMPLE 22 NI,Nl-Dimethyi-4-methoxybenzene-1,2-disuifonamide Using a procedure analogous to that described in Example 10, 58.0 g of the product of Example 21 was converted to 34.8 g of NI,Nl-dimethyi-4methoxybenzene-1,2-disuifonamide, m.p. 106-911.

NMR(DMSO-d,)8:

2.8 (s, 5.9H, -NMe2); 3.9 (s, 3.1 H, OCH3); 7.0-8.1 (m, 5.0H, 5 aromatics + S02NH2 EXAMPLE 23 25 N'(Butylaminocarbonyi)-N,N-dimethyi-4-methoxy)-1,2benzenedisuifonamide Using a procedure analogous to that described in Example 11, 33.0 g of the product of Example 22 was converted to 43.0 g of N'- (butylaminocarbonyf)-N,N-dimethyi-4-methoxy-1,2-benzenedisulfonamide, obtained as a viscous oil. NMIR(DiVISO-c1JS:

0.6-1.5 (m, 8.7H, 8 butyl hydrogens); 2.6-3.1 (m, 7.6H, 2 butyl hydrogens + NMe2); 3.85 (s, 2.7H, OCH3); 63-7.0 (broad t, 0.7H, CH2NH); 7.2-8.1 (m,'2.7H, 3 aromatics); -9.8 (broad, 0.7H, NH).

EXAMPLE 24 N,N-Dimethyi-2-(isocyanatosuifonyi)-4methoxybenzenesuifonamide Using a procedure analogous to that described in Example 12, 19.7 g of the product of Example 23 was converted to 16.0 g of N,N-dimethyi-2- (isocyanatosuifonyi)-4-methoxybenzenesuffonamide, 40 obtained as a viscous oil.

EXAMPLE 25

N 2-[(4-M ethoxy-6-m ethyl pyri midin-2-yi)a m inocarbonyll-N 1,N 1-di methyl-4-methoxy 1 2 -benzenedi sulfonamide Using a procedure analogous to that described in Example 13, 2.7 of the product of Example 24 was converted to 1.2 g of N 2_[(4-methoxy-6-methylpyrimidin-2yl)aminocarbonyll-NI,Nl-dimethyi-4- 45 methoxy-1,2-benzenedisuffonamide, m.p. 205-70 (d).

NIVIR(DIVISO-d')S:

2.4 (s, 3.1 H, Het-CH,); 2.8 (s, 6.1 H, N Mej; 3.9 (s, 6.1 H, 2 OCH3'S) 6.5 (s, 1.0H, Het-H); 73-8.1 (m, 3.0H, 3 aromatics); 10.5 (s, 0.9H, NI-1); 13.5 (broad, 0.8H, NH).

EXAMPLE 26

N-Methy]-N-[ 1, 1,2,2-tetrafluoroethyi)-2-nitrobenzenesuffonamide A solution of 72 g of N-methyi-2-nitrobenzenesuifonamide, 35 g of tetrafluoroethylene and 4 g of powdered potassium hydroxide in 150 mi of dimethylformamide was heated at 851 for 3 hours in a pressure vessel. The reaction mixture was cooled to 251' and poured into 800 mi of water. A heavy oil - 26 GB 2 057 429 A 26 was separated and the aqueous layer extracted with 150 mi of of 1- chlorobutane. The heavy oil, the 1chlorobutane extract and an additional 300 mi of 1 -chlorobutane were combined and washed three times with water. The organic solution was dried over magnesium sulfate and concentrated in-vacuo to yield 85.1 g of N-methyl-N-(1,1,2,2-tetrafluoroethyl)-2- nitrobenzenesuifonamide as a viscous orange 5 oil. NMR(DCD'3)8:

11-3.3 (m, 2.6H, N-CH3); 5.2-7.3 (tt, 1.01-1, JFC1-1=57Hz and JKCH=51-1z, CF,W; 73-8.3 (m, 4.41-1, 4 aromatics).

EXAMPLE27 N-Methy]-N-(1,1,2,2-tetrafluoroethyl)-2aminobenzenesuifonamide Using a procedure analogous to that described in Example 15, 82.0 g of the product of Example 26 was converted to 65.4 g of N-methyi-N-(1,1,2,2tetrafluoroethyi)-2-aminobenzenesuifonamide, as a viscous oil.

NMR(CDC[3)8:

2.9 (t J=31-1z, 2.71-1, CH3NCF-); 4.5 T5.4 (broad, 1.9H, N1-1j; 5.4-5.6 and 6.4-7.8 (m, 5.41-1, 4 aromatics + CF,H).

EXAMPLE 28 20 N-Methyi-N-(1,1,2,2-tetrafluoroethyi)-1,2benzenedisuifonamide Using a procedure analogous to that described in Example 10, 60.0 g of the product of Example 27 was converted to 32.0 g of N-methy]-N-(1,1,2,2- tetrafluoroethyi)-1,2-benzenedisuifonamide, m.p. 102-1070. NMR(DMSO-d,)8:

3.3 (broad singlet, 2.91-1, CH,N); 6.05, 6.95, 7.85 (tt, 1.01-1, CF21-1); 7.5 (broad singlet, 1.81-1, S02NI-12); 7.9-8.7 (m, 4.31-1, 4 aromatics).

Anal. Calcd. for C,1-11,N.04S2F4: C, 30.86; H, 2.88; N,8.00.

Found: C, 31.1; H, 2.82, N, 8.01. 30 31.2 2.69 8.04 EXAMPLE 29

NI-(Butylaminocarbonyi)-N-methyl-N-(1,1,2,2-tetrafluoroethyi)-1,2benzenedis ulfonamide Using a procedure analogous to that described in Example 11, 24.5 g of the product of Example 28 was converted to 31.0 g 6f N'-(butylaminocarbonyi)-N-methyi-N-(1,1,2,2- tetrafluoroethyi)-1,2benzenedisuifonamide, m.p. 146-1520.

NMR(DMSO-d,)&:

0.6-1.5)m, 7.21-1, 7 butyl hydrogens); 23-3.1 (m, 2.01-1, 2 butyl hydrogens); 3.1-3.3 (s, 2.7 H, CHA; 5.9, 6.85, 7.75 (tt, 1.01-1, CF2H); 6.65 (t 1.01-1, CH-NH) 7.9-8.5 (m, 4.3 H, 4 a ro m aties); 10.2 (s, 0.81-1, NH).

EXAMPLE 30 N-Methyl-N-(1,1,2,2-tetrafluoroethyi)benzenesuifonylisocyanate Using a procedure analogous to that described in Example 12, the product of Example 29 was converted to N-methy]-N-(1,1,2,2tetrafluoroethyl)benzenesuifonylisocyanate, isolated as a viscous oil.

IR(Neat): 2230 cm (S02NCO).

EXAMPLE 31

NI R4-M ethoxy-6-m ethyl pyri m idin-2 -yi) am inoca rbonyll-N-methyl -N(1, 1,2,2-tetrafl uoroethyi)- 1,2 benzenedisuifonamide A mixture of 3.1 g of the product of Example 30, 0.8 g of 2-amino-4- methyi-6-methoxy pyrimidine and a few crystals of DABCO in 15 mi of acetonitrile was stirred at 501 for 1 hour and at 250 overnight. The precipitate was filtered off, washed with acetonitrile and dried to give 1.9 g of WAW 55 methoxy-6-methylpyrimidin-2-yi)aminocarbonyll-N-methyi-Ntetrafluoroethyi)-1,2-benzenedisuifon- amide, m.p. 176-1770 (d).

27 GB 2 057 429 A 27 Anal. Calcd. for C,,H17F4N.O.S2 NMR(DMSO-d,)8:

C, 37.28; H, 3.32; N,13.59.

Found: Q 3 7.3; H, 3.3 7; N,13.8.

37.3 3.35 13.8 2.3 (s, 2.9H, Het-CH.); 3.2 (broad singlet, 2.9, CH,-M; 3.9 (s, 2.9H, Het-OCH3); 5.9, 6.8, 7.7 (tt, 0.9H, CF2W; 6.65 (s, 1.0H, Het-H); 8.0-8.7 (m, 4.411, 4 aromatics); 10.7 (s, 1.0H, NW; 13.9 (broad singlet, 0.9H, NFI).

EXAMPLE 32 N-(Phenyimethoxy)-2-nitrobenzenesuifonamide A solution of 96.4 g of 0-benzyihydroxylamine in 80 mi of tetrahydrofuran was added to a solution15 of 86.8 g of o-nitrobenzenesuifonyl chloride in 400 mi of tetrahydrofuran at 5-101. After stirring at ambient temperature for 16 hours the solvent was evaporated. The residue was washed with water, filtered and dried to give 112.6 g of N-(phenyimethoxy)-2-nitrobenzenesulfanamide, m.p. 148-151 EXAMPLE 33 20 N-Methyi-N-(phenyimethoxy)-2-nitrobenzenesuifonamide A mixture of 110.6 g of the product of Example 32, 49.8 g of anhydrous potassium carbonate, 55.8 g of methyliodide and 500 mi of acetone was stirred at ambient temperature for 20 hours. The solvent was evaporated and the residue partitioned between methylene chloride and water. Concentration of the organic extract afforded 88.9 g of N-methyi-N(phenyimethoxy)-2-nitrobenzene- suifonamide as a yellow oil. [NMR: 8 2.8 (s, 3H, NCH,fl.

EXAMPLE 34

N-Methyi-N-(phenyimethoxy)-2-aminobenzenesuifonamide To a solution of 88.9 g of the product of Example 33 in 565 mi of 90% aqueous acetic acid was added 83 g of iron powder at 80-901 in several portions. Wat& (60 mi) was then added and heating continued for 20 minutes. Charcoal (10 9) was added and the solution filtered through Celitee and 30 concentrated in vacuo. The residue was made strongly alkaline with 20% NaOH solution, then extracted with methylene chloride. The extract was dried and concentrated in-vacuo to give 29.3 g of N-methyl N-(phenyimethoxy)-2-aminobenzenesuifonamide as a yellow oil.

[NMR:8 5.1 (broad singlet, 211, NHA' EXAMPLE 35 N-Methy]-N-(phenyimethoxy)-1,2-benzenedisuifonamide Using a procedure analogous to that described in Example 10, 28.8 g of the product of Example 34 was converted to 19.3 g of N-methyi-N(phenyimethoxy)-1,2benzenedisuffonamide, m.p.

122-128. [NMR:8 5.7 (broad singlet, 2H, S02NHJ].

EXAMPLE 36

NI-(Butylaminocarbonyll-N-methyi-N-(phenyimethoxy)-1,2benzenedisulfonamide Using a procedure analogous to that described in Example 11, 18.8 g of the product of Example 45 was converted to 19.1 g of N-(butylaminocarbonyi)-N-methyi-N- (phenyimethoxy)-1,2-benzenedisulfonamide, obtained as a brown syrup.

EXAMPLE 37 W4K6-Di methyl pyri midi n-2 -yi)a m inocarbonyll-N-m ethyl -N(phenyl methoxy) 1,2-benze nedi- sulfonamide Using a procedure analogous to those described in Examples 12 and 13, 18. 6 g of the product of Example 36 was converted to 7.4 g of W-[(4,6-di methyl pyri m idin-2 yi)a m i noca rbonyl I-N-methy]-N (phenyl methoxy)1,2-benzenedisuifonamide, m.p. 186-19211.

NMIR(DiVISO-d')S:

2.4 (s, 6H, Het-CH3'S); 2.8 (s, 3H, C1-13N); 4.7 (s, 2H, CH,O); GB 2 057 429 A 28 7.1 (s, 1 H, Het-H); 7.3 (s, 5H, 5 aromatics); 7.8-9.0 (m, 4H, 4 aromatics); 10.4 (broad S, 1 H, NH); 13.7 (brbad S, 1 H, NW.

EXAMPLE 38 NI-[(4,6-Dirn ethylpyri midin-2-y0a m inocarbonyll-N-m ethyl1,2-benzenedisu Ifona mide To a suspension of 0.5 9 of the product of Example 37 in 10 mi of dry xylenes was added 0.5 mi of borontribromide dropwise. The resultant thick suspension was warmed to 601 for 1 hour. The reaction mixture was cooled to room temperature, quenched with water and triturated with hexanes. The resultant suspension was filtered and air dried to give 0.3 9 o.I'N '-[(4, 6-di methyl pyri m idin-2-y1)a m i nocarbonyll-N-methyi-1,2- benzenedisuifonamide, m.p. 180-1850. The NMR showed the complete loss of the phenyimethoxy group.

IR(Nujol) 1715 cm-1 W=O), 1360 cm-1 (SO,).

Mass Spect.

M/e = 187 M/e 149 NH H 2C. 3 so 2 NH 2) C N 0 H 3 N _ (0 CH 3 -EXAMPLE 39

N'[(4,6-Dimethoxy-1,3,5-triazin-2-yi)thioxomethylaminol-N,N-diethyl-1,2ben zenedisuifonamide A mixture of 4.0 g of N,N-diethyi-1,2-benzenedisuifonamide, 2.7 g of anhydrous potassium carbonate, 5.8 9 of 4,6-dimethoxy-1,3,5-triazin-2-isothiocyanate, and 60 mi of dry acetone was stirred 20 at ambient temperature for 18 hours. A precipitate was filtered off, washed with acetone, then suspended in 350 mi of water and brought to pH=1 with 1 N HIC1 solution. The precipitate was filtered, washed with water and dried 3 hours at 601 in-vacuo to give 3.0 g of N'[(4,6-dimethoxy-1,3,5-triazin2-yl)thioxomethylaminol-N,N-diethyi-1,2-benzenedisuifonamide, m.p. 1541560 (d).

NIVIRMMSO-d6W 0.9-1.2 [5, 5.7H, (CH3CH2)2N-I; 3.11-3.5 [qt. 4.5H, (CR3CH2)2N-I; 3.8 (s, 5.9H, Het-OCH3'S); 7.5-8.7 (m, 4.0H, 4 aromatics); 9.1 (s, 0.9H, NW.

*1 EXAMPLE 40

Methyl N'-[2-(diethylaminosuifonyi)phenyisuifonyll-N-(4,6-dimethoxy-1,3,5triazin-2 -yi)carbamimido- thioate A mixture of 2.0 g of the product of Example 39, 25 mi of tetrahydrofuran and 1.5 mi of 3M sodium methoxide in methanol solution was refluxed for 10 minutes. A solution of 0.8 g of methyl 35 iodide in 10 mi of tetrahydrofuran was added and the mixture refluxed for another 2 hours. The solution was cooled to 200, filtered and stripped in-vacuo to give 3 g of viscous oil. The oil was triturated with mi of 1 -chlorobutane and filtered again. The filtrate was stripped again to give 1.3 g of oil which slowly crystallized. This solid was triturated with 50:50 cyclohexane/l - chlorobutane and filtered to give 0.5 g of crude product. Recrystallization from acetonitrile gave 0.18 g of methyl N'-[2-(diethylarnino- 40 suifonyf)phenyisuifonyi)-N-(4,6-dimethoxy-1,3,5-triazin-2yi)carbamidothioat e, m.p. 150-1561.

Anal. Calcd. for C17H24N.O.S3 Found NIVIR(DIVISO-ddS:

1.0-1.3 [t, 5.7H (CH3CH,),N-L 2.2 5 (s, 3.1 H, CH3S) - - 3.2-3.6 [qt, 4.4H, (i:H.CH2)2N-I; 4.0 (s, 5.8H, Het-OCH3'S); 7.91-8.7 (m, 4.1 H, 4 aromatics); 10.9 (broads, 1.0H, NW.

C, 40.47; H, 4.79; N,16.65.

C, 40.8; H, 4.81; N,17.4.

41.0 4.87 17.5 so 29 GB 2 057 429 A 29 Using the methods and examples discussed above, and choosing the appropriate aminoheterocycle and sulfonyl isocyanate or sulfonyl isothiocyanate, the compounds described in Tables 1 to IV-a can be prepared.

Also, using the methods and examples discussed above, the sulfonylisocyanates and 5 sulfonylisothiocyanates described in Table V can be prepared.

Table I so 2 NR 2 R 3 R1 2 3 IR 1 11, - R a H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH H 4-Br CH 3 H 4-Br CH 3 X W N so 2-c- 0 R R D 4 5 NJ \ y R 2 R 3 4 CH 3 CH 3 H CH 3 CH 1 H CHJ' CH3 H CH 3 CH 3 CH 3 CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CS 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H CH 3 CH 3 H 3 CH 3 H CH 3 H H CH 3 H H H R W X y H 0 H 0 H 0 H 0 CH 3 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 H 0 11 0 H 0 OCE 3 OCH 3 CH 3 OCH 3 OCH 3 H CH 3 CH 2 0 CH 3 0 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CS 3 CH 3 CH 3 CH 3 0 CH 3 0 0 CH 3 0 0 CH 3 m. P. CO OCH 3 CH 3 CH 3 OCH 3 CH 3 H CH 3 CF 3 NHCH 3 N (CH 3)2 CF 3 CH 2 0 CH 3 CH 2 0 SCH 3 CH 3 O(CH P2 0 c 2 H 5 O(CH P3 0 CH 3 O(CH P2 CH 3 OCH 2 OCH 2 CO 2 CH 3 OCH 2 CO 2 c 3 H 7 OCHCO 2 CH 3 178-1830 CH 3 OCHCO C H 1 2 2 5 CH 3 CH 3 CH 3 228-230'(d) 235-237'(d) 219-222(d) 177-181'(d) 197-199(d 212-2130(d) GB 2 057 429 A 30 Table I (continued) R! R R 2 R 3 R 4 R 5 W X y M.P.CO 0 11 H a CH 3 CH 3 H H 0 CH 3 OCH CN(CH 3)2 H R CH 3 CH 3 R H 0 CH 3 OCKN(C 3 H 7)2 1 CH 3 H a CH 3 CH 3 H H 0 H cil 3 H H CH 3 CH 3 H H 0 CH 3 OCHCO 2 i-C 3 H 7 CH 3 H 4-Cl CH 3 CH 3 H H 0 CH 3 CH 3 0 218-2210 H 4-Br CH 3 CH 3 R H 0 CH 3 0 CH 3 0 200-2020 H 4-F CH 3 CH 3 H H 0 CH 3 0 CH 3 0 202-204'(d) H 4-CH 3 CH 3 CH 3 H H 0 CH 3 CH 3 0 216-2180(d) H 4-C 3 H 7 CH 3 CH 3 H H 0 CH 3 CH 3 0 H 4-NO 2 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 2112130(d) H 4-W 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 194-196 H 4-NH 2 ca 3 CH 3 H H 0 CH 3 CH 3 0 185190'(d) H 4-N(CH 3)2 CH 3 CH 3 H H 0 CH 3 CH 3 0 H 4-CN CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH 3 S- CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH3S- CH CH H H 0 CH 0 CH 0 It 3 3 3 3 0 0 of H 4-CE S- CH CH a H 0 CH 0 CH 0 3te 3 3 3 3 0 H 4-CH 3 0 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 191.3-192.50(d H 3-Cl CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 5-F CH 3 CH 3 R H 0 CH 3 0 CH 3 0 H 6-Cl CR3 CH 3 R H 0 CH 3 0 CH 3 0 H H c 2 R 5 c 2 H 5 R H 0 CH 3 0 CH 3 0 190-192 H H C2 H 5 c 2 H 5 H H 0 CH 3 CH 3 0 170-172 H H c 2 H 5 C2S H H 0 CH 3 CH 3 176-1790 H a c 2 H 5 c 2RS " H S CH 3 0 CH 3 0 H H C2 H 5 c 2 H 5 H H S CH 3 CH 3 0 H 4-C 2 H 5 0 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 181-184'(d) H 4-C 2 H 5 0- CH 3 CH 3 H H 0 CH 3 0 CH 3 205-2080(d) H 4-C 2 H 5 0- CH 3 CH 3 H H 0 CH 3 CH 3 190-1930(d) v 31 GB 2 057 429 A 31 Table I (continued) R 1 R 2 R 3 R 4 R 5 W X y P. (0 H H n-C 3 H 7 n-C 3 E7 H H 0 CH 3 0 CH 30 163-165 H H n-C 3 H 7 n-C 3 H 7 H H 0 CH 3 0 CH 3 189-194 H H n-C 3 H 7 CH 3 H H 0 CH 3 0 CH 30 glass H H n-C 3 H 7 CH 3 H H 0 CH 3 0 CH 3 glass H H sec-C 4 H 9 CH 3 H H 0 CH 3 0 CH 30 203-207 H H sec-C 4 H 9 CH 3 H H 0 CH 3 0 CH 3 188-1910 H H n-C 4 H 9 CH 3 H H 0 CH 3 0 CH 3 0 146-1490 H H n-C 4 H 9 CH 3 H H 0 CH 3 0 CH 3 138-1420 H H i-C 3 H 7 i-C 3 H 7 H H 0 CH 3 0 CH 30 187-189 H H i-C 3 H 7 i-C 3 H 7 H H 0 CH 3 0 CH 3- 190-192 H H CH 2-CHCH 2- CH 2CHCH 2- H H 0 CH 3 0 ca 3 0 H H n-C 6 H 13 CH 3 H H 0 CH 3 0 CH 3 0 H H >- CH 3 H H 0 CH 3 0 CH 3 0 H H 0- CH 3 H H 0 CH 3 0 CH 3 0 H H (:)- C113 H H 0 CH 3 0CH 3 0 H 1' (:- CH3 H H 0 CH 3 0 CH 3 0 H H 1:-CH CH 3 H H 0 CH 3 0CH 3 0 CH 3 H H NC-C- CH 3 H H 0 CH 3 0 CH 3 0 H H H NCCE 2- KCH2- H H 0 CH 3 0 CH 3 0 H H NCCH 2 CH 2- NCCE 2CH2- H H 0 CH 3 0 CH 3 0 H H CH 3 0 (CH P2- CH 3 0 (CH P2 H H 0 CH 3 0 CH 3 0 H H CH 3 OCE-CH 2- CH 3 OCH-CH 2- H H 0 CH 3 0 CH30 E 3 ia 3 32 GB 2 057 429 A 32 Table I (continued) RI R R R R R W X y m. P. Cc) - 1 2 3 4 5 R H n-C 6H13 R-C4S H H 0 CH 3 0 CH 3 0 H H CH 3 0 CH 3 H H 0 CH 3 0 CH 3 0 207-211 H H -CH 2 co 2 CH 3 -CH 2 co 2 CH 3 H H 0 CH 3 0 CH 3 0 H H -CHCO 2 CH 3 -HCO 2 CH 3 H H 0 CH 3 0 CH 3 0 CH 3 CH 3 H -CR 2 co 2 -CH 2 co 2 H 11 0 CH3 0 CH 3 0 0 0 or 91 H H -CH 2 W (CH 3) 2 -CH 2 W (CH 3) 2 H H 0 CH 3 0CH 3 0 0 1 c 0 of H -CH 2 W (C 3 H 7) 2 -CH 2 CN(C 3 H 7)2 H H 0 CH 3 0 CH 3 0 0 0 11 to H H -CH-CN(CH -CH-CN(CH H H 0 CH 0 CH 0 H 3 3 ii 3 3 2 3 3 H H -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 220-222(d) H H -CH 2 CH 2 CH 2 ck 2- H H 0 CH 3 0 CH 3 0 227-229(d) H H -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 CH 3 213-215c(d) H 4-Cl -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 H 4-CF 3 -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 H H -(CH 2) 5- H H 0 CH 3 0 CH 3 0 201-204 H E -(CH 2) 6- H H 0 CH 3 0 cii 3 0 glass H H -(CH 2) 2-0-(CH 2) 2- H H 0 CH 3 0 CH 3 0 199-2040 H H & CR 3 H H 0 CH 3 0 CH 3 183-1860 1 H E Cl-& CH 3 a H 0 CH 3 o', CH 3 H H CHf& CH3 H H 0 CH 3 0 CH 3 H a Br CH 3 H H 0 CH 3 0 CH 3 H H F CH3 R H 0 CH 3 0 CH 3 33 GB 2 057 429 A 33 Table I (continuedl R,' R, R 2 R 3 R 4 R 5 W X Y M. P. (c) H H &CH 2- CH 3 H H 0 CH 3 0 CH 3 179-1830(d) H H CH- CH IR H 0 CH 0 CH &V 3 3 3 CH 3 H H ci-.CH,- -CH 3 H H 0 - CH 3 0 CH 3 H 11 CH3-@CH 2- -CH 3 H H 0 CH 3 0 CH 3 H Cl-& H- -CH 3 H H 0 CH 3 0 CH 3 CH 3 H H H F CH 2- CH 3 H H 0. CH 3 0 CH 3 H H Br H- CH H H 0 CH 0 CH 3 3 3 CH 3 H 4-Cr CH CH H H 0 CH 0 CH 182-1850(d) 3. 3 3 3 3 H 4-CF 3 CH 3 CH 3 H H 0 CH 3 CH 3 190-192(d) H 4-Cl CH 3 CH 3 H H 0 CH 3 0 CH 3 0 200-2050 H 4-Cl CH 3 CH 3 H H 0 CH 3 CH 3 ' 223-226 H 4-Cl c 2 H 5 cos H H 0 CH 3 0 CH 3 0 187-1900 H 4-Cl c 2 H 5 c 2 H 5 H H 0 CH 3 0 CH 3 179-1810 H 4-Cl30 CH 3 CH 3 H H 0 CH 3 0 CH 3 205-2070(d) H 4-CH 3 0 CH 3 CH 3 H H 0 CH 3 CH 3 206-207(d) 5-Cl.4-Cl CH 3 CH 3 H H 0 CH 3 0 CH 3 0 5-F 4-Cl CH 3 CH 3 H H 0 CR 3 0 CH 3 0 5-Br 4-Cl CH 3 CH 3 H H 0 CH 3 0 CH 3 0 5-CH 3 4-CH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 5-CH 3 0 4-CH 3 0 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 6-Cl 4-Cl CH 3 CH 3 H H 0 CH 3 0CH 3 0 4-Cl 3-Cl CH 3 CH 3 H H 0 CH 3 0CH 3 0 34 GB 2 057 429 A 34 Table I (continued) R! R R 2 R 3 R 4 R 5 W X Y E. P. co 4-F CH 3 CH 3 H H 0 CH 3 0 CH 3 222-224(d) H 4-F CH 3 CH 3 H H 0 CH 3 CH3 218-219(d) H 4-CH 3 CH 3 CH H H 0 CH 3 0 CH 3 0 208-2100(d) fl 4-CH 3 CH 3 CH 3 H H 0 CH 3 CH 3 202-2150(d) H 4-NO 2 CH 3 CH 3 H H 0 CH 3 0 CH 3 207-2090(d) H 4-NO 2 CH 3 CH 3 H H 0 CH 3 CH 3 212-2150(d) H 4-NH 2 CH 3 CH 3 H H 0 CH 3 0 CH 3 H 4-bli 2 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-N(CH 3 2 CH 3 CH 3 H H 0 CH 3 0 CH 3 H 4-N(CH 3 2 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-W CH 3 CH 3 H H 0 CH 3 0 CH 3 H 4-CN CH3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3 S_ CH 3 CH 3 H H 0 CH 3 0 CH 3 H 4-CH 3 S_ CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3 so 2- CH 3 CH 3 H H 0 CH 3 0 CH 3 H 4-CH 3 so 2- CH 3 CH 3 H H 0 CH 3 CH 3 H 4-N-C-0 CH3 CH 3 H H 0 CH 3 0 CH 3 0 0 If H 4-NHCCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 I H 4-n.HCCH(CH 3 2 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 el H 4-',iHCNECH 3 CH 3 CH 3 H H 0 CH 3 0CH30 0 et H 4-.\'RCNHCH(CH 3) 2 CH 3 Cii 3 H H 0 CH 3 0 CH30 H H CH CH H H 0 CH -OCHCO2H 3 3 3 1 CH3 H CH 3 CH 3 H H 0 CH 3 -C02CH3 H CH 3 Cil 3 H H 0 CH 3 C02H H H CH 3 CH 3 H H 0 CH 3 C02-< H H CH 3 CH 3 H H 0 CH 3 CH2CO2CH3 H H CH 3 CH 3 H H 0 CH 3 CH2CO.) H H CH 3 CH 3 H H 0 CH 3 CH2CO2H GB 2 057 429 A 35 Table I (continued) R 1 R 2 R 3 R 4 R 5 W X y M. P. (0 H H CH 30 CH 3 H H 0 CH 3 0 CH 3 220-223 H H CH 3 0 CH 3 H H 0 CH 3 CH 3 220-222 H CH 3 CE2 CH 3 H H 0 CH 3 0 CH 3 0 204-2060 H H CH 3 CH 2 CH 3 H H 0 CH 3 0 CH 3 200-202 H H CH 3 CH 2 CH 3 H H 0 CH 3 CH 3 192-194 H a n-C H CH H H 0 CH CH 173-176 3 7 3 3 3 H H n-C 3 H 7 CH 3 H H 0 CH 3 0 CH 3 0 202-205 H H i-C 3 H 7 CH 3 H H 0 CH 3 0 CH 3 192-200 H H i-C 3 H 7 CH 3 H H 0 CH 3 CH 3 193-196 H H n-C H CH H H 0 CH CH 173-176 1 4 9 3 3 3 H H sec-C 4 H 9 CH 3 H H 0 CH 3 CH 3 184-188 H ii & CH 3 H H 0 CH 3 0 CH 3 0 138-180 H H & CH3 H H 0 CH 3 CH 3 184-1850 H H & CH 2- CH 3 H H 0 CH 3 0 CH 3 0 178-181(d) H H &CHi- CH3 H H 0 CH 3 CH 3 188-1900(d).

H H i-C 3 H 7 c 2 H 5 H H 0 CH 3 0 CH 3 0 207-209 H H i-C 3 H 7 c 2 H 5 H H 0 CH 3 0 CH 3 171-174 H H i-C 3 H 7 c 2 H 5 H H 0 CH 3 CH 3 168-171 a H i-C 3 R 7!-c 3 H 7 H H 0 CH 3 CH 3 208-2110 H H -(CR Ps- H H 0 CH 3 0 CH 3 209-2110 H H -(CH Ps- R H 0 CH 3 CH 3 179-182 H R -CH 2 CH 2 OCH 2 CH 2- H H 0 CH 3 0 CH 3 218-2230 H H -CH 2 CH 2 OCH 2 CH 2- H H 0- CH 3 CH 3 209-211 H R -(CH P6- H H 0 CH 3 0 CH 3 169-171 li R -(CH P6- H H 0 CH 3 CH 3 190-192 H R n-c 3 H 7 R-C 3 H 7 H H 0 CH 3 CH 3 180-184 36 GB 2 057 429 A 36 Table I (continued) R R 2 R 3 R4 R5 W X Y M. P. C) 0 91 R 4-CCH 3 CH 3 CH 3 H H 0 CH 3 CH 3 0 H 4-c il-C 3 H 7 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 2 OCH 3 CH 3 CH 3 H H 0 CH3 CH 3 H 4-CH 20--:'-C3 H 7 CH3 CH 3 H H 0 CH 3 CH 3 H 4-CH 2 SCH 3 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 2 so 2 CH 3 CH 3 CH 3 H H 0 CR3 CH 3 H 4-CH SCE CH CH H H 0 CH CH 399 3 3 3 3 3 0 H ii H H CH 3 H H 0 CH 3 0..CH 3 0 -CH 2-0 CH 3' H H 0 CH 3 0CH 3 0 C11 3 CH 3 H H 0 CH 3 0 -CR 2 CH 3 CH 3 CH 3 H H 0 CH 3 0 -CH 2 CH 2 CH 3 H H CH 3 CH 3 H H 0 CH 3 0 -CH(CH 3)2 37 GB 2 057 429 A 37 Table I (continued) RI R, R 2 R 3 R 4 R 5 W X y P. (00 R H H CH 3 H H 0 CH 3 0 CH 3 H H H c H H H 0 CH 3 0 CH 3 H H H n-C 3 H 7 H H 0 CH 3 0 CH 3 H H H i-C 3 H 7 H H 0 CH 3 0 CH 3 H H H n-C 4 H 9 H H 0 CH 3 0 CH 3 H H H t-C 4 H 9 H H 0 CH 3 0 CH 3 H H H sec-C4 H 9 H H 0 CH 3 0 CH 3 H H H CH 2-CHCH 2- H H 0 CH 3 0 CH 3 H H H -CH 2 co 2 CH 3 H H 0 CH 3 0 CH 3 H H H -n-C 6 H 13 H H 0 CH 3 0 CH 3 H H &CH 2 0- CH 3- H H 0 CH 3 0 CH 3 H H &Ho- CH 3 H H 0 CH 3 0 CH 3 CH 3 H H PCH 20- CH3 H H 0 CH 30 CH 3 cl H H PCH 20- CH 3 H H 0 CH 30CH 3 CH 3 H H W 3 CH 2- W 3 CH 2- H H 0 CH 3 0 CH 3 H H -CH2 CECH CH 3 H H 0 CH 3 0 CH 30 H3 H H -C-CQCH CH 3 H H 0 CH 3 0 CH 3 0 H 3 H H CH 3- CF 3 CHFU 2- H H 0 CH 3 0 CH 3 H H CH 3- RBrFCCF 2- H H 0 CH 3 0 CH,( H H CH 3- HClKW 2- H H 0 CH3 0 CH 3 H H CH 3- HW 2 CF 2 11 H 0 CH 3 0 CH 3 176-177(d) H H CH 3HU 2 W 2- H H 0 CH 3 0 CH 3 0 179-181'(d) H H CH3- HU 2 W 2- H H 0 CH 3 C3 171-i810(d) 38 GB 2 057 429 A 38 Table I (continued) R! R R 2 R 3 R 4 R 5 W X y m. P CC) 0 R 4-NHCOCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-NHCO-1-C 3 H 7 CH 3 CH 3 H H 0 CH 3 0CH 3 H H CH 3 CH 3 H H 0 CH 3 0 -CH 2 CN H H CH 3 CH 3 H H 0 CH 3 0 -CH 2 CH 2 W H H CH 3 CH 3 H H 0 CH 3 0 -CH 2 cl H H CH 3 CH 3 H H 0 CH 3 0 -N 3 H H CH 3 CH 3 H H 0 CH 3 0 -OCH 2 CH=CH 2 H H CH 3 CH 3 H H 0 CH 3 0 -OCH 2 CúCH H CH CH H H 0 CH 0 -N-CH CN 3 3 3 1 2 CH 3 1 39 GB 2 057 429 A 39 Table I-a so 2 A X R' W 1 N 3 If so 2-C-N 0 P R 4 '5 y R1 Rl % R5 W X y M. P. (C) CF 3 CH 2 0- H H H R 0 CH 3 0 CH 3 o 203-2030 CF 3 CH 2 0- H H H H 0 CH 3 0 CH 3 191-192(d) W 3 CH 2 0- H H H H 0 CH 3 CH 3 187-188.50(d) 00 _ 0- H H H H 0 CH 3 0 CH 3 o 219-2220(d) 0- H H H H 0 CH 3 0 CH 3 210-215(d) 0- H H H a 0 CH 3 CH 3 192-194'(d) Ccl 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 Ccl 3 CH 2 0- H H H H 0 CH 3 0 CH 3 Ccl 3 CH 2 0- H H H H 0 CH 3 CH 3 CBr 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 CR 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 W 2 CR 2 0- H R H H 0 CH 3 0 CH 3 0 CF 3 CF 3 CR 2 0- H H E H 0 CH 3 0 CH 3 0 CP 3 M P2 CR 2 0H H H H 0 CH 3 0 CH 3 0 CF 3 SHO- H R H a 0 CH 3 0 CH 3 0 CH 3 (W 3)2 CROH a H H 0 CH 3 0 CH 3 0 (CF 3)2 CHO- H H H H 0 CH 3 0 CH 3 (CF 3)2 CRO- H a H R 0 CH 3 CH 3 cl-& 0- H H H H 0 CH 3 0 CH 3 0 GB 2 057 429 A 40 Table I-& (continued) A RI R 1 R4 W X y R-'P - -C C) CHf& 0- 11 R a R 0 CH 3 0 CH 3 0 CR 3 0-&0- H H R 0 CSo C1SO 02 N-& o- ii ll R 0 CH 3 0CH 3 0 CF 3 CH 2 0 H 4-Cl H H 0 CH3 0 CH 3 0 W 3 CH 2 0 H 4-CF 3 H H 0 CH 3 0 CH 3 0 W 3 CH 2 0 H 4-CH 30 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-NO 2 H R 0 CH 3 0 CH 3 0 CF 3 CH 20 H 4-CN H H 0 CH 3 0 CH 3 0 W 3 CH 20 H 4F H H 0 CH 3 0 CH 3 0 CF3 CH 2 0 H 4-CN H R 0 CH 3 0 CH 3 0 1 41 GB 2 057 429 A 41 Table I-b

R 1 so 2 A X SB N 6 9 2- so 2 N=C-NH 0 g43 N) y 1 R 1 A B X 1 Y1 m. P. ec) H -N(CH 3)2 CH 3 H -N(CH 3)2 I-C3 H7 H -N(CH 3?2 R-C6 H 13 H -N(CH P2 CH30CH 2 CH 2 H -N(CH 3)2 c 2 H 5 OCH 2 CH 2 H -N(CH 3)2 CH 3 O(CH P3 H-N(CH 3)2 c); 3 0 2 CCH 2 H -N(CH 3)2 -i-C3 H 702CCH 2 H -N(CH 3)2 CH 3N, c (0) C14. 2 OCH CH 3- CH 3 0 CH3- CH30 CH3- CH 30 CH 3- CHP CH 3- CH 3 0 CH 3- CH 3 0 CH 3- CH 30 CH 3- CH30 CH3- C1130 3 H -N(CH 3)2 (CH 3)2 NC(OCH 2- CH 3- CH 3 0 H -N(CH 3)2 (CH 3 CH 2 CH P2 NC(OCH 2- CH 3- CH 3 0 H -N(CH 3)2 H2 NC(OCH 2- CH 3- CH 3 0 H -N(CH 3)2 H 2- CH 3- CH 3 0 H -N(CH 3Y2 0 CH 2- CH 3- CH 3 0 P7 cl H -N(CH 3)2 KCH2- CH 3- CH 3 0 H -N(CH 3)2 H 3 C-CHCH 2- CH 3- CH 3 0 B -N(CH P2 HCIECCH 2- CH 3- CH 3 0 H -N(CH P2 CH 3 OCH 2- CH 3- CH 3 0 H -N(CH P2 CH 3 (CH P3 OCH 2- CH 3- CH 3 0 H -N(CH 3)2 CH 3 O(CH P2 OCH 2- CH 3- CH 3 0 H -N(CE P2 c 2RS O(CH P2 OCH 2- CH 3-CH 3 0 42 GB 2 057 429 A 42 Table I-b (continued) R 1 A B X 1 y 1 M.P.CO H -N(C 2 H 5) 2 CH 3 CH 3 0 CH3P H -N-C 2 H 5 CH 3 CH 3 0 CH 3 H 3 H -N-i-C 3 H 7 CH 3 CH 3 0 CH 3 H 3 H -N-n-C 6 H 13 CH 3 CH 3 0 CH 3 CH 3 H -N-CH 2-e CH 3 CH 3 0 CH 3 CH 3 H -N-OCH 2 0 CH 3 CH 3 0 CH 3 ii 3 H -NHCH 3 CH 3 CH 3 0 CH 3 H -NHC 2 H 5 CH 3 CH 3 0 CH 3 H -NHC 6 H 13 CH 3 CH 3 0 CH 3 H -N-CF 2 W 2 H CH 3 CH 3 0 CH 3 CH 3 H -OCH 2 CF 3 CH 3 CH 3 0 CH 3 H -N) CH 3 CH 3 0 CH 3 H -N-CH W CH CH 0 CH 1 2 3 3 3 CH 3 H -N(CH 2 CN) 2 CH 3 CH 3 0 CH 3 4-Cl -N(CH 3)2 CH 3 CH 3 0 CH 3 4-W 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-NO 2 -N(CH 3) 2 CH 3 CH 3 0 CH 3 4-CE 3 0 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-F -N(CH 3)2 CH 3 CH 3 0 CH 3 4-Br -N(CH 3)2 CH 3 CH 3 0 CH 3 4-CH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-CN -N(CH 3)2 CH 3 CH 3 0 CH 3 43 GB 2 057 429 A 43 Table I-b (continued) R A B X 1 y P. CO 4-N (CH 3)2 -N (CH 3)2 CH 3 CH 3 0 CH 3 4-SCH 3 -N (CH 3) 2 CH 3 CH 3 0 CH 3 4-50 2 CH 3 -N (CH 3) 2 CH 3 CH 3 0 CH 3 4-NH 2 -N (CH 3)2 CH 3 CH 3 0 CH 3 0 4-N'HCCH 3 -N (CH 3)2 CH 3 CH 3 0 CH 3 0 4-NHUHCH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 0 4-IMCOCH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 R -N(CH 3)2 CH 3 CH 3 0CH 3 0 H -N(CH 3)2 CH 3 CH 3 CH 3 H -N(CH 3)2 CH 3 H CH 3 H -N(CH 3)2 CH 3 H CH 3 0 H -N(CH 3)2 CH 3 H c 2 H 5 0 H -N(CH 3)2 CH 3 CH 3 c 2 H 5 0 H -N(CH 3)2 CH 3 CH 3 0 c 2 H 5 0 0 of H -N(CH 3) 2 CH 3 HNCCH 2- CH 3 CH 3 0 0 H -N(CH 3)2 CH 3 CH 2 HNCCH 2- CH 3 CH 3 0 0 H N(CH 3)2 (CH 3)2 CHNHCCF. 2CH 3-' CH 3 0 44- GB 2 057 429 A 44 Table I i so 2 NR 2 R 3 RI k 2 1 W N so 2-C- 0 N R 4 R 5 N y Ri '1 R2 '3 R 4 R 5 W X y M. P. (c) CH 3, CH 3 H H 0 OCR 3 OCR 3 200-203@(d) R H CHS CH3 H H 0 OCH3 CH 3 194-196'(d) H H CH 3 CH 3 H H 0 CH 3 CH 3 210-212'(d) H H CH 3 CH 3 CH 3 H 0 OCR 3 OCR 3 H H CH 3 CH 3 H CH 3 0 OCR 3 OCR 3 167-170'(d) H H CH 3 CH 3 H H 0 H H H H CH 3 CH 3 H H 0 CH 3 CH 2 0 CH 3 H H CH 3 CH 3 a H 0 CH 3 0 W 3 H H CH 3 cH 3 H H 0 CH 3 NHCH 3 H H CH 3 CH 3 H 9 0 CH 3 N(CH 3)2 H H cH 3 CH 3 H H 0 CH 3 W 3 CH 20 glass H H CH 3 CH 3 H H 0 CH 3 0 CH 3 CH 20 163-1-670 H CR CH H a 0 CH SCH 3 3 3 3 H H CH 3 CH 3 H H 0 CH 3 CH 3 O(CH P2 0 H H CH CH H H 0 CE, C H O(CH) 0 3 3 3 2 5 2 3 H H cH 3 CH 3 H H 0 CH 3 CH 3 O(CH P2 H H CH 3 CH 3 H a 0 CH 3 CH 3 OCR 2 H H cH 3 CH 3 H H 0 CH 3 OCR 2 CO 2 CH 3 179-186'(d) R H CH 3 CH 3 H H 0 CH 3 OCR 2 co 2 c 3 a 7 H R CS CH R H 0 CH OCHCO CH 3 3 3 v 2 3 CH 3 H M CH 3 CH 3 a a 0 CH 3 0 OCHCO 2 c 2 H 5 H 3 H 4-Br CH 3 CH 3 H H 0 CH 3 0 CH 3 193-195'(d) H 4-Br CH 3 CH 3 H H 0 CH 3 CH 3 213-214'(d) GB 2 057 429 A 45 Table II(continued) RI R, R 2 R 3 R 4 R 5 W X y m. P. CO 0 #g H a CS 3 CS 3 H H 0 CS 3 OCH 2 W (CH 3)2 p H a CH 3 CS 3 H H 0 CS 3 OCHW (C 3 H 7) 2 C11 3 H CS 3 CS 3 H H 0 H CS 3 H CS CS H H 0 CS OCHCO 3 3 3 1 21-C3S7 CS 3 H 4-Cl CS 3 CS 3 R H 0 CS 3 CS 3 0 193-1980 H 4-Br CS 3 CS 3 H H 0 CS 3 0 CS 3 0 199.5-2000(d) H 4-P CS 3 CS 3 H H 0 CS 3 0 CH 3 0 169-1750(d) H 4-CH 3 CS 3 CS 3 H H 0 CS 3 CS 3 0 207-209 0 (d) 11 4-C 3 H 7 CS 3 CS 3 H H 0 CS 3 CS 3 0 H 4-NO 2 CS 3 CH 3 H H 0 CH 3 0 CS 3 0 184-1860(d) H 4-CP 3 CS 3 CS 3 H H 0 CS 3 0 CS 3 0 157-1670 H 4-NH 2 CS 3 CS 3 H H 0 CS 3 CS 3 0 175-1850(d) H 4-N(CH P2 CS 3 CS 3 H H 0 CS 3 CS 3 0 H 4-CN CS 3 CS 3 H H 0 CS 3 0 CS 3 0 H 4-CH 3 SCS 3 CS 3 H H 0 CS 3 0 CH 3 0 H 4-CH S- CS CS E H 0 CS 0 CH 0 391 3 3 3 3 0 0 @g H 4-CH S- CS CS H E 0 CS 0 CS 0 311 3 3 3 3 0 H 4-CE30 CS 3 CS 3 H H 0 CS 3 0 CS 3 0 186.5-189'(d) H 3-Cl CS 3 CS 3 H H 0 CS 3 0 CS 3 0 H 5-F CS 3 CS 3 H a 0 CS 3 0 CS 3 0 H 6-Cl CS 3 CS 3 H E 0 CS 3 0 CS 3 0 H H c 2 H 5 c 2 H 5 H E 0 CS 3 0 CS 3 0 175-177c H 5 C2 H 5 c 2 H 5 R H 0 CS 3 CS 3 0 170-1760 H a c 2 H 5 c 2 H 5 E H 0 ca 3 CS 3 179-1810 H E c 2 H 5 c 2 H 5 R 5 S CS 3 0 CS 3 0 H M C2R 5 c 2 H 5 S E S CE3 CS 3 0 H 4-NH 2 CS 3 CH 3 H H 0 CS 3 0 CH 3 0 175-1850(d) H 4-C 2 H 5 0- CH 3 CS 3 H H 0 CH 3 0 CH 3 0 180-1830(d) H 4-C 2 H 5 0- CS 3 CH 3 H H 0 CS 3 0 CH 3 179-1810(d) R 4-C 2 H 5 0- CS 3 CS 3 H H 0 CS 3 CS 3 170-1800(d) 46 GB 2 057 429 A 46 Tible II(continued) R,' R, R 2 R 3 R 4 RS W X y M'P'('C) H n-C 3 H 7!L-C 3 E7 H a 0 CH 3 0 CH 3 0 110-165 H a n-C P7 a-CP7 H H 0 CH 3 0 CH 3 glass H H n-C P7 CH 3 H H 0 CH 3 0 CH30 glass H a - CH H - H 0 CH 0 CH 170-1720 n-CP7 3 3 3 H H sec-C 4 H 9 CH 3 H H 0 CH 3 0 CH 3 0 glass H H sec-C 4H 9 CH 3 H H 0 CH 3 0 CH 3 glass H H n-C 4 H 9 CH 3 H R 0 CH 3 0 CH 3 0 H H n-C 4 H 9 CH 3 H H 0 CH 3 0 CH 3 123-134 H H i-C 3 H 7!-c 3 H 7 H H 0 CH 3 0 CH 30 glass H H i-C 3 fl 7 i-C 3 H 7 H H 0 CH 3 0 CH 3- 167-174 H H CH 2-CHCH 2- CH 2-CHCH 2- H H 0 CH 3 0 CH 3 0 H H n-C 6H13 CH 3 H H 0 CH 3 0 CH 3 0 H CHj H H 0 CH 3 0 CH 3 0 H CH 3 H R 0 CH 3 0 CH 3 0 11 CH 3 H H 0 CH 3 0CH 3 0 H R H R CH 3 CH l 3 H H NC-CE 3 H R NCCE - CH CH CH H H 0 CH 3 0 H H 0 CH 3 0 H R 0 2 NCCH 2- H H 0 H R KCH 2 CH 2- NCCH 2 CH 2- H H 0 H R CH 3 O(CH P2- CH 3 O(CH P2 H H 0 H H CH OCE-CH - CH OCR-CE - H H 0 3 v 2 3 2 2 CH 3 CH 3 H H CH 3 CH 2- CH 3 CH 2- H H S a CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CHio CH 3 0 CH 3 0 CH 3 0 CH 3 0154-156'(d) 47 GB 2 057 429 A 47 Table II(continued) R,' R 1 R 2 R 3 R 4 R 5 W X y H H H H n-C 6 H 13 n-C 4 H 9 H H 0 CH 3 0 CH 3 0 H H CR 3 0 CH 3 H H 0 CH 3 0 CH 3 0 190-194 H a -CH 2 co 2 CH 3 -CH 2 co 2 CH 3 H H 0 CH 3 0 CH 3 0 H H -CHCO 2CS -ECO 2 CH 3 H H 0 CH 3 0 CH 3 0 R 3 CH 3 H a -CH 2 co 2. -CH 2 co 2 H H 0 CH 3 0 CH 3 0 0 0 If $g -CH 2 CN(CH 3) 2 -CH 2 CN(CH 3) 2 H m 0 CH30CH 3 0 0 0 It 91 R -CE. CN (C H) -CH, 2 CN(C 3 H 7) 2 H H 0 CH 3 0 CH 3 0 2 3 7 2 0 0 It go H H -H-CN(CH -CH-CN(CH a H 0 CH 0 CH 0 3 2 3 2 3 3 CH 3 CH 3 H H -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 H H -CH 2 CH 2 CH 2 CH 2 H M 0 CH 3 0 CH 3 208-210(d) H H -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 CH 3 217-219c(d) H 4-Cl -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 H 4-CF 3 -CH 2 CH 2 CH 2 CH 2- H H 0 CH 3 0 CH 3 0 H M -(CR 2) 5- H H 0 CH 3 0 CH30 197-199' H H -(CR P6- H H 0 CH 3 0 CH 3 0 glass H H -(CH 2)270-(CH P2- H H 0 CH 3 0 CH 3 0 173-1770 H H @_ CH 3 H R 0 CH 3 0 CH 3 180-183 H 8 Cl-& C113 R H 0 CH 3 0 CH 3 H a CHf& CH 3 R H 0 CH 3 0 CH 3 H H Br CH 3 H R 0 CH 3 0 CH 3 H 2 F -@- C113 R a 0 CH 3 0CH 3 48 GB 2 057 429 A 48 Table Il(continued) R ' R 1 R 2 a a H H H H H H H H H H H H H 5-cl 5-F 5-Br 5-CH 3 5-CH 3 0 6-Cl 4-Cl R 3 R 4 R 5 W &CH 2- 9 & H- CH 3 a Cl- Cl'2_ CHCH 3 C11,- H Br -@- H- CH 3 4-W 3 CH 3 4-CF 3 CH 3 4-cl CH 3 4-Cl CH 3 4-Cl c 2 H 5 4-Cl c 2 H 5 4-CR 3 0 CH 3 4-CH30 C3 4-Cl CH 3 4-Cl CH 3 4-Cl CH 3 4-CH 3 CH 3 4-cR 3 0 CH 3 4-Cl CH 3 3-Cl CH 3 X yM. P. C0 CH 3 H H 0 CH 3 0 CH 3 CH 3 H H 0 CH 3 0 CH 3 -CH 3 H H -CH 3 H H 0 CH 3 0 CH 3 0 CH 3 0 CH 3 -CH 3 H H 0 CH 3 0 CH 3 H H 0 CH 3 0 H l a 0 CH 3 0 H H H H H H H H H H H H H H H H H H H H H H R CH 3 CH 3 0 CH 3 0 CH 3 0 CH 3 CH 3 0 CH 3 0 CH 3 0 0 CH 3 CH 3 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 CH 3 0 CH 3 0 CH 3 CH 3 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 0 CH 3 0 CH 3 0 182-1840(&) 175-1800 194-1970(d) 194-1970 219-2220 190-1950(d) 170-1810 193-1950(d) 183.5-185 4 49 GB 2 057 429 A 49 Table II(continued) R,' R R 2 R 3 R 4 R 5 W X y M. P. (cc) H 4-F CH 3 CH 3 H H 0 CH30 CH 3 177-188(d) H 4-F CH 3 CH 3 H H 0 CH 3 CH3 210-212'(d) H 4-CH CH CH H H 0 CH 0 CH 0 202-2040(d) 3. 3 3 3 3 H 4-CH 3 CH 3 CH 3 H H 0 CH 3 c P. 3 210-213(d) H 4-NO 2 CH 3 CH 3 H H 0 CH 3 0 CH3 180-184(d) H 4-NO 2 CH 3 CH 3 H H 0 CH 3 CH3 188-192M H 4-NiH 2 CH 3 CH 3 H H 0 CH 3 0 CH3 H 4-NH 2 CH 3 CH 3 H H 0 CH 3 CH3 H 4N(CH 3) 2 CH 3 CH 3 H H 0 CH 3 0 CH3 H 4-N(CH 3) 2 CH 3 CH3 H H 0 CH 3 CH3 H 4-M CH 3 CH 3 H H 0 CH 3 0 CH3 H 4-CN CH 3 CH 3 H H 0 CH 3 CH3 H 4-CH'S- CH CH H H 0 CH 0- CH 3 3 3 3 3 H 4-CH 3 S_ CH 3 CH 3 H H 0 CH 3 CP.3 H A-CH 3 SO 2CH 3 CH 3 H H 0 CH 3 0 CH3 H 4-CH 3 so 2- CH 3 CH 3 H H 0 CH 3 CH3 H 4-N-C-0 CH3 CH 3 H H 0 CH 3 0 CH3 0 0 H 4-NHCCH 3 CH 3 CH 3 H H 0 CH 3 0 CH30 0 H 4-MCCH(CH 3)2 CH 3 CH 3 H H 0 CH 3 0 CH30 0 H 4-NHCiNHCH 3 CH 3 CH 3 H H 0 CH 3 0 CH30 0 H 4-NliClilICH (CH 3)2 CH 3 CH 3 H H 0 CH 3 0 CH30 CH CH3 H H 0 CH -OCHCO 2H 3 3 1 CH3 H H CH 3 CH 3 H H 0 CH 3 -C02CH 3 H H CE 3 CH 3 H H 0 n 3 C02F.

H H CH 3 CH 3 H H 0 CH 3 C02-< H H CH 3 CH 3 R 9 0 CH 3 CH2CO2CH3 H H CH 3 CH 3 H H 0 CH 3 CH2C02 H a CH 3 CH 3 H H 0 CH 3 CH2CO2H GB 2 057 429 A 50 Table Mcontinued) RI R, R2 R 3 R 4 R 5 W X y m. P. CC) R R CH 3 0 CH 3 H H 0 CH 30 CH 3 182-1860 9 H c OS CH 3 H H 0 CH 3 0 CH 3 0 179-180 H H C 2 H r, CH 3 H H o CH 30 CH 3 189-1920 H H R-C 3 H 7 CH 3 H H 0 CH 3 CH 3 144-147 H H i-C 3 H 7 CH 3 H H 0 CHIO CH 3 0 215-2170 H H i-C 3 H 7 CH 3 H H 0 CH 3 0 CH 3 181-1950 H H i-C 3 H 7 CH 3 H H 0 CH 3 CH 3 187-190 H H n-C 4 H 9 CH 3 H H 0 CH j 0 CH 3 0 H R n-C H CH H H 0 CH CH 113-1160 4,9 3 3 3 H H sec-,C 4 H 9 CH 3 H H 0 CH 3 CH 3 glass.

H H C'S H H 0 CH 3 0 CH 3 0 114-1160 H 1' CH3 H H 0 CH 3 CH 3 189-191.

H H cc CH 2 CH 3 H H 0 CH 3 0 CH 30 179-183(d) 11 71 &CH 2 CH 3 H H 0 CH 3 CH 3 171-175'(d) 1' H & Cl'2 CH3 1' 1' 0 Cl'3 Cl'3 H H i-C 3 H 7 C 2 H 5 H H 0 CH30CH 3 0 170-1850 H R i-C 3 H 7 c 2 H 5 H H 0 CH 3 0 CH 3 162-1700 H H I-C 3 H 7 c 2 H 5 H H 0 CH 3 CH 3 161-1640 H H n-C 3 H 7 a- C 3 H 7 H H 0 CH 3 CH 3 H n i-C 3 H 7!-c 3 H 7 H H 0 CH 3 CH 3 196-1980 H H - (CH PsH H 0 CH 3 0 CH 3 191-1950 H H - (CH PS- Ii H 0 CE3 CH3 197-201 H H -CH 2 CH 2 OCH 2 CH 2- H H 0 CH 3 0 CH 3 209-212 H H -CH 2 CH 2 OCH 2 CH 2- H H 0 CH 3 CH 3 192-1990 H H - (CH P6- H H 0 CH 3 0 CH 3 glass H H - (CH P6- H H 0 CH 3 CH 3 184-1860 -n 51 GB 2 057 429 A 51 Table Mcontinued) % R 1 R 2R 3 R 4 RS W X Y M. P. (0 H H H CH 3H H 0 CH 3 0 CH 3 H H H C 2 H 5 H 11 0 CH 3 0 ch 3 H H H n-C 3 H 7 H H 0 CH 3 0 CH 3 H H H i-C 3 H 7 H H 0 CH 3 0 CH 3 H H H n-C 4 H 9 H H 0 CH 3 0 CH 3 H H H t-C 4 H 9 H H. 0 CH 3 0 CH 3 H H H sec-C 4 H 9H H 0 CH 3 0 CH 3 H a H CH 2-CHCH 2- H H 0 CH 3 0 CH 3 H H H -CH 2 co 2 CH 3 H H 0 CH 3 0 CH 3 H H H -n-C6 H 13 H H 0 CH 3 0 CH 3 H H & CH 2 0- CH 3- H H 0 CH 3 0 H H &clio- CH 3 H H 0 CH 3 0 CH 3 CH 3 H H PCH 20- CH3 H H 0 CH 30 CH3 cl H H PCH 20- CH3H H 0 CH 30 CH3 CH 3 H H W CH C? CH H H 0 CH 0 M 3 2- 3 2- 3 H H CH 3-cr 3 CHFCF27 H H 0 CH 3 0 CH 3 H H CH 3- HBrFCCP 2- H H 0 CH 3 0 CH 3 H H CH 3- HUF= 2- H H 0 CH 3 0 CH 3 H H CH 3- HU 2 cr 2- H H 0 CH 3 0 CH 3 171-173(d) H H CH 3- HCF 2 CF 2-H H 0 CH 3 0 CH 30 155-1570(d) HHCH 3-HU 2 CF 2- HH0CH 3CH 3184-188(d) 52 GB 2 057 429 A 52 Table II(continued) 1 R,' R 2 3 R 4 5 W X y M.P. (C) 0 R 4-IMCOCH 3 CH 3 M 3 H H 0 CH 3 0 CH 3 0 H 4-1,',IHCO-i-C 3 H 7 CH 3 CH 3 H H 0 CH 3 0CH 3 H CH 3 CH 3 H H 0 CH 3 0 -CH 2 M H CH 3 CH 3 H H 0 CH 3 0 -CH 2 CH 2 W H CH 3 CH 3 H H 0 CH 3 0 -CH 2 cl H H CH 3 CH 3 H H 0 CH 3 0 -N 3 H H CH 3 CH 3 H H 0 CH 3 0 -OCH 2 CH-CH 2 H CH 3 CH 3 H H 0 CH 3 0 -OCH 2 CLECH H CH 3 CH 3 H H 0 CH 3 0 -N-CH 2QN H 3 0 %% CH H 4-CCH 3 C11 3 CH 3 H H 0 CH 3 3 0 11 CH CH H H 0 CH CH H 4-c-i-c 3 H 7 3 3 3 3 H 4-CH 2 OCH 3 CH 3 CH 3 H H 0 CH3 CH 3 H 4-CH 20.-'-C3 H 7 CH3 CH3 H H 0 CH 3 CH 3 H 4-CH2 SCH 3 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 2 so 2 CH 3 CH 3 CH 3 H H 0 CR3 CH 3 H 4-CH SCH CH CH H H 0 CH CH 201 3 3 3 3 3 0 Table II (continued) ' R, R R R R4 R_5 W X -1 1 2 3 H H -CH 2 CECH CH 3 H H 0 CH 3 0 H H -C(CH 3) 2 C2CH CH 3 H H 0CH 3 0 y m. P. (C) CH 3 0 CH 3 0 H H -CH2-'G CH3 H H 0 CH P CH30 H H -CH2-9:Q CH3 H H 0 CH30 CH 30 H H CH 3 CH 3 H H 0 CH 3 0 -CH 2 CH 3 H H CH 3 CH 3 H H 0 CH 3 0 -CH 2 CH 2 CH 3 H H CH 3 CH 3 H H 0 CH 3 0-CH(CH 3) 2 1 53 GB 2 057 429 A 53 Table II-a so 2 A Re W N 3 il SO 2 N-C-N 0 N N:: y X % R, R4 R5 W X y P. CC) A -- - - - - W 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 194-196(d) CF 3 CH 2 0- H H H H 0 CH 3 0 CH 3 189-190(d) cr 3 CH 2 0- H H H H 0 CH 3 CH 3 186-189(d) 0- H H H H 0 CH 3 0 CH 3 0 190-194c(d) 0- H H H H 0 CH 0 CH 191-1930(d) 3 3 00 0- H H H H 0 CH 3 CH 3 199-2. 010 (d) CC1 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 CC1 3 CH 2 0- H H H H 0 CH 3 0 CH 3 CC1 3 CH 2 0- H H H H 0 CH 3 CH 3 CBr 3 CR 2 0- H H H H 0 CH 3 0 CH 3 0 Ecr 2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 cr 2 CR 2 0- H 11 H H 0 CH 3 0 CH 3 0 cr 3 cr 3 CR 2 0- H H H H 0 CH 3 0 CH 3 0 C- (CF) CR 0- R H. H H 0 CH 0 CH 3 2 2 2 3 3 CF 00- H H H m 0 CH 3 0CH 3 0 CH 3 (CF P2 CHG- H H H H 0 CH 3 0 CH 3 0 (cr P2 CHO- H a H H 0 CH 3 0 CH 3 (CF P2 CHO- H H H H 0 CH 3 CH 3 cl-& 0- 11 11 H H 0 CH 3 0 CH 3 0 54...

GB 2 057 429 A 54 Table II-a (continued) R' R R R X y A 4 5 W 1 1 m. P. C0 CH,-&0- H H H H 0 CH 3 0 CH 3 0 CH 3 0-& 0- H H H H 0 CH 3 0 CH 3 0 0 2 N-&0_ H H H H 0 CH 3 0CH 3 0 W 3 CH 2 0 H 4-Cl H H 0 CH 3 0 CH 3 0 W 3 CH 2 0 H 4-CF 3 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-CH 3 0 H H 0 CH3 0 CH 3 0 W 3 CH 2 0 H 4-NO 2 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-CN H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-F H H 0 CH 3 0 CH 3 0 W 3 CH20 H 4-CH 3 H H 0 CH 3 0 CH 3 0 ox GB 2 057 429 A 55 Table II-b so 2 A R 1 N 2 - so 2 N=C-NH- 0 N it 3 jg N X 1 y 1 R 1 A B X 1 y 1- M.P.CO H -N (CH 3)2 CH 3- CH 3- CH 30 H -N(CH 3)2 i-C 3 H 7- CH 3- CH 30 H -N (CH P2 a-C6"13- CH37 CH 3 0 H -N(CH)2 CH 3 OCH 2 CH 2- CH3- CH3P H -N(CH 3)2 C2H.OCHP'2_ CH 3- CH 30 H -N(CH 3)2 CH 3 O(CH P3- CHj- CH30 H -N(CH 3)2 C14 3 0 2 CCH 2- CH 3- CH30 H -N(CH 3)2 i-C 3 H 7 0 2 CCH 2- CH3- CH30 H -N(CH 3)2 CH 3 NCM04.27 CH3CH 30 OCH 3 H -N(CH 3)2 (CH 3)2 NC(OCH 2- CH 3- CH 3 0 H -N(CH) (CH CH CH NC(OCH CH - CH 0 3 2 3 2 2 2.2 3 3 H -N(CH P2 H 2 NC(OCH 2 CH3- CH 30 H -N(CH 3)2 &-CH 2- CH 3- CH 3 0 H -N(CH 3)2 -N(CH P2 -N(CH P2 -N(CH P2 -N (CH P2 -N(CH 3)2 -N(CH P2 -N (CH P2 H -N(CH P2 CH 2,7C1 NCCH 2H 2C.MCHCH 2ECIECCH 2CH 3 OCH 2CH3CH2)30C"2CH 3 O(CH P2 OCH 2c 2 H 5 O(CH P2 OCH 2R CH 3 HNCCH 2- 0 9 9 H -N(CH 3)2 CH 3 CH2MCCH 20 H -N(CE3)2 (CH 3)2 CHUCCE2- CH3- CH30 CH3- CH30 CH 3- CH 3 0 CH 3- CH 3 0 CH 3- CH 3 0 CH 3CH 3 0 CH 3- CH 3 0 CH 3- CH 3 0 CH 3- CH 3 0 CH 3- CH 3 0 CH 3- CH 3 0 56 GB 2 057 429 A 56 Table II-b (continued) R 1 A B X 1 y 1 M.P.CO a -N(C 25)2 CH 3 CH 3 0 CH 3 0 R -N-C H CH CH 0 CH 1 2 5 3 3 3 CH 3 H -N-i-C H CH CH 0 CH - 3 7 3 3 3 CH 3 H -N-n-C CH CH 0 CH 9 01:3 3 3 3 CH 3 H -N-CH CH CH 0 CH 2 3 3 3 CH 3 H -N-OCH 7e CH CH 0 CH 91 2 3 3 3 CH 3 H -NHCH 3 CH 3 CH 3 0 CH 3 H -MC 2 H 5 CH 3 CH 3 0 CH 3 H -NHC 6 H 13 CH 3 CH 3 0 CH 3 H -N-CF 2 W 2 H CH 3 CH 3 0 CH 1 3 CH 3 H -OCH 2 W 3 CH 3 CH 3 0 CH 3 H -NC) CH 3 CH 3 0 CH 3 H -N-CH M CH CH 0 CH 1 2 3 3 3 CH 3 H -N(CH 2 W) 2 CH 3 CH 3 0 CH 3 4-Cl -N(CH P2 CH 3 CH 3 0 CH 3 4-CF 3 -N(CH 3)2 CH3 CH 3 0 CH 3 4-NO -N(CH) CH CH 0 CH 2 3 2 3.3 3 4-CE 3 0 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-F -N(CH P2 CH 3 CH 3 0 CH 3 4-Br -N(CH 3)2 CH 3 CH 3 0 CH 3 4-CH 3 -N(CH P2 CH 3 CH 3 0 CH 3 4-M -N(CH P2 CH 3 CH 3 0 CH 3 57 GB 2 057 429 A 57 Table II-b (continued) R 1 B X 1 y 1 4-N(CH P2 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-SCH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 4-SO 2 CH 3 -N(CH 3)2 CH3 CH30 CH 3 4-NH 2 -N(CH 3)2 CH 3 CH 3 0 cii 3 0 4-NHCCH 3 -N(CH 3)2 CH3 CH 3 0 CH 3 0 4-NHWHCH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 0 4-NHCOCH 3 -N(CH 3)2 CH 3 CH 3 0 CH 3 H -N(CH P2 CH 3 CH 3 0 CH 3 0 H -N(CH 3)2 CH 3 CH 3 CH 3 H -N(CH 3)2 CH 3 H CH 3 H -N(CH 3)2 CH 3 H CH 3 0 H -N(CH 3)2 CH3 H c 2 H 5 0 H -N(CH 3)2 CH 3 CH 3 c 2 H 5 0 H -N(CH P2 CH 3 CH 3 0 c 2 H 5 0 M. P. CO.

58 GB 2 057 429 A 58 Table III so 2 NR 2 R 3 R' 1 W 2 3 R 1 N l\ SO --N N 2 0 R 4 R 5 X 1 y 1 R 1 R2 R 3 R 4 R 5 W X 1 y 1 m. P. C0 R H CH 3 CH 3 H H 0 H CH 3 0 H H CH 3 CH 3 H H 0 a CH 3 H H CH 3 CH 3 H H 0 H c 2 H 5 0 H R CH 3 CH 3 H H 0 CH 3 CH 3 189-1930 (d) H H CH 3 CH 3 H H 0 CH 3 CH 3 0 H H CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H H CH 3 CH 3 CH 3 H 0 CH 3 CH 3 H H CH 3 CH 3 H CH 3 0 CH 3 CH 3 H H CH 3 CH 3 H H S CH 3 CH 3 H H CH 3 CH 2- CH 3 CH 2- H H 0 CH 3 CH 3 H H -(CH P4- H H 0 CH 3 CH 3 H 4-Cl - (cr, 2) C H H 0 CH 3 CH 3 H 4-W 3 CH 3 CH 3 H H 0 CH 3 CH 3 0 H 4-CH S- CH CH H H 0 CH CH 391 3 3 3 3 0 H 4-M CH 3 CH 3 H H 0 CH 3 CH 3 H H CH 2mCHCH 2- CH 2mCHCH 2- H H 0 CH 3 CH 3 H H - (CH 2) 2-0-(CH 2) H H 0 CH 3 CH 3 H 4-NO 2 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3 0 CR 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3CH 3 CH 3 H H 0 CH 3 CH 3 H 3-Cl CH 3 CH 3 R a 0 CR 3 CH 3 H H n-C 6 H 13 CH 3 H H 0 CH 3 CH 3 H H NCCE 2 CH 2- NCCE 2 CH 2- H H 0 CH 3 CH 3 H H CH 2 co 2 CH 3 CH 2 co 2 CH 3 H H 0 CH 3 CH 3 lc i 59 GB 2 057 429 A 59 Table III (continued) R, R 2 R 3 R 4 R 5 W X 1 y 1 m. P. C0 H 4-NCO CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 #1 H 4-NWCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 to H 4-NiliCCH(CH 3)2 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 H 4-NH-CNHCH 3 CH 3 CH 3 H H 0 CH 3 0CH 3 0 0 H 4-NHWTHCH (CH 3 2 CH 3 CH 3 H H 0 CH 3 0CH 3 0 0 H 4-NHCOCH 3 CH 3 CH 3 H H 0 CH 30CR30 0 H 4-NHCO-i-C 3 H 7 CH 3 CH 3 H H 0 CH 3 0CH 3 0 0 H 4-CCH 3 CH 3 CH 3 H 1,1 0 CH 3 0CH 3 0 H 4-CH 2 OCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH 2 SCH 3 CH 3 CH 3 H H 0 CH3 0 CH 3 0 H 4-CH 2 so 2 CH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H H -W 2 W 2 H CH 3 H H 0 CH 3 0 CH 3 0 GB 2 057 429 A 60 Table III (continued) R,' R R 2 R 3 R 4 R 5 W 1 1 M.P. (C) CH 3 H H 0 CH 3 0 CH 3 H 2 H c H H H 0 CH 3 0 CH 3 H H H n-C 3 H 7 H H 0 CH 3 0 CH 3 H H H i-C 3 H 7 H H 0 CH 3 0 CH 3 H H H a-c H H H 0 CH 3 0 CH 3 H H H t-C 4 H 9 H H 0 CH 3 0 CH 3 H H H sec-C 4 H 9 H H 0 CH 3 0 CH 3 H H H CH 2mCHCH 2- H H 0 CH 3 0 CH 3 H H H -CH 2 co 2 CH 3 H H 0 CH 3 0 CH 3 H H H -n-C 6 H 13 H H 0 CH 3 0 CH 3 H H & CH 2 0- CH 3- H H 0 CH 3 0 CH 3 H H &CHO- CH H H 0 CH 0 CH 9 3 3 3 CH 3 H H PC1T_ C'SH H 0 CH 30 CH 3 cl H H PCH20- CH3 H l' 0 CH30CH 3 CH 3 H H W 3 CH 2 W 3 CH 2- H H 0 CH 3 0 CH 3 H 13 CH 3- cr 3 CHFU2- H H 0 CH 3 0 CH 3 R R CH 3- HBrRU 2- H H 0 CH 3 0 CH 3 H H CH 3 - H=CU 2- H H 0 CH 3 0 CH 3 H H CH 3 - HW 2 W 2- H H 0 CH 3 0 CH 3' H H CH 3 - HU 2 CF 2- H H 0 CH 3 0 CH 3 0 H H CH 3 - HU 2 W 2- H H 0 CH 3 CH 3 61 GB 2 057 429 A 61 Table III (continued) R! R 1 0 R 2 R 114 RS W X, 11 3 H 4-NHCOCH 3 CH 3 CH 3 H H 0 CH 3 0CH 3 0 0 H 4-NHCO-i-C 3 H 7 CH 3 H H H H CH 3 H H 0 CH 3 0 -CH 2 C2CH CH 3 H H 0 CH3 0 -C(CH P2 Cr.CH CH 3 H H 0 CH 3 0 CH 3 CH 3 CH 3 H H -CH 2---'1CH 3 H H 0 CH 3 0 CH 3 H H -CH 2-0 CH 3 H H 0 CH 3 0CH 3 62 GB 2 057 429 A 62 Table Ill-a so 2 A R! W 3 11 SO N-C-N 21 1 R 4 RS y X 1 1 R? Rl % "S W X, M.P. (C) A 1 - - - - Al cr 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 W 3 CH 2 0- H H H H 0 CH 3 0 CH 3 W 3 CH 2 0- H H H H 0 CH 3 CH 3 0- H H H H 0 CH 3 0 CH 3 0 0- H H H H 0 CH 3 0 CH 3 cci 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 eci 3 CH 2 0- H H H H 0 CH 3 0 CH 3 CC13 CH 2 0- H H H H 0 CH 3 CH 3 CBr 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 W 2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 W 3 CF 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 CF 3 (W P2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 cr CHO- H H H H 0 CH 0 CH 0 31 3 3 CH 3 (CF 3)2 CHO- H H H H 0 CH 3 0 CH 3 0 (CF 3)2 CEO- H H H H 0 CH 3 0 CH 3 (CF 3)2 CHO- H H H H 0 CH 3 CH 3 Cl-& 0- H H H H 0 CH 3 0 CH 3 0 63 GB 2 057 429 A 63 Table III-a (continued) A R! R 1 R4 R 5 W X - - - -1 CH3-& 0H H H H 0 CH30 CH30 CH 3 0-& 0- H H 9 H 0 CH 3 0 CH 3 0 0 2 1,T-& 0- H H H H 0 CH30 CH30 CF 3 CH2 0 H 4-Cl H H 0 CH3 0 CH 3 0 cr 3 CH20 H 4-CF 3 H H 0 CH 3 0 CH 3 0 CF 3 CH20 H 4-CH 3 0 H H 0 CH3 0 CH 3 0 CF 3 CH20 H 4-NO2 H H 0 CH 3 0 CH 3 0 CF 3 CH20 H 4-CN H H 0 CH 3 0 CH30 CF 3 CH20 H 4-F H H 0 CH 3 0 CH3 0 CF 3 CH20 H 4-CH 3 H H 0 CH3 0 CH30 Yl -m.P.CC) 64 GB 2 057 429 A 64 Table IV

SO 2 NR 2 R 3 1 R,' '. 3 2 W N ig so --N y R 1 OD - X 1 & 9 R 4 R5 N-N R,' R R 2 R 3 R 4 R 5 W X 1 y P. (c) CH 3 CH 3 H H 0 H CH 3 0 H H CH 3 CH 3 H H 0 H CH 3 H H CH 3 CH 3 H H 0 H c 2 H 5 0 H R CH 3 CH 3 H H 0 CH 3 CH 3 glass H H CH 3 CH 3 H H 0 CH 3- CH 3 0 H m CH 3 CH 3 H H 0 CH 3 0CH 3 0 H H CH 3 CH 3 PH 3 H 0 CH 3 CH 3 H H CH 3 CH 3 H CH 3 0 CF. 3 CH 3 H H CH 3 CH 3 H H S CH 3 CH 3 H H c 2 H 5 c 2 H 5 H H 0 CH 3 CH 3 H H -(CH 2)4_ H H 0 CH 3 CH 3 H 4-Cl -(CH P4- H H 0 CH 3 CH 3 H 4-CF 3 c 2 H 5 c 2 H 5 H H 0 CH 3 CH 3 0 It H 4-CH S- CH CH H a 0 CH CH 311 3 3 3 3 0 H 4-CN CH 3 CH 3 H H 0 CH 3 CH 3 H H CH 2-CHCH 2- CH 2mcHCH 2- H H 0 CH 3 CH 3 H a -(CH P2-0-(CH 2 H H 0 CH 3 CH 3 H 4-NO 2 CH 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3- ca 3 CH 3 H H 0 CH 3 CH 3 H 4-CH 3 0 CH 3 CH 3 H H 0 CH 3 CH 3 H 3-Cl CH 3 CH 3 R H 0 CH 3 CH 3 H R n-C 013 CS H H 0 CH 3 CH 3 H R NCCE 2 CH 2- NCCH 2 CS 2- H H 0 CH 3 CH 3 H R CH 2 co 2 CH 3 CH 2 co 2 CH 3 R H 0 CH 3 CH 3 GB 2 057 429 A 65 Table IV (continued) R 2 R 3 R4 P5 W Xl '1 m.P.CO 4-NCO CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 g H 4-NHCCH 3 CH 3 CH 3 H H 0 CH 3 0CH 3 0 0 It H 4-,XHCCH(CH 3)2 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 H 4-MN.HCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 0 H 4-NHCNHCH(CH P2 CH 3 CH3 H H 0 CH 3 0 CH 3 0 0 of 0 CH 0 H 4-NHCOCH 3 CH 3 CH 3 H H 0 CH 3 3 0 #g H CH CH H H 0 CH 0 CH 0 H 4-NHCO-i-C 3 7 3 3 3 3 0 #I H 4-CCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH 2 OCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH 2 SCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-CH 2 so 2 CH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 66 GB 2 057 429 A 66 Table IV (continued) RI p X y R 2 R 3 RS W 1 1 m. P. C0 H H H CH 3 H H 0 CH 3 0 CH 3 H H H c H H H 0 CH 3 0 CH 3 H H H n-C 3 H 7 H H 0 CH 3 0 CH 3 H H H i-C 3 H 7 H H 0 CH 3 0 CH 3 H H H n-C 4 H 9 H H 0 CH 3 0 CH 3 H H H!-C H H H 0 CH 3 0 CH 3 H H H sec-C 4 H 9H H 0 CH 3 0 CH 3 H H H CH 2-CHCH 2- H H 0 CH 3 0 CH 3 H H H -CH 2 CO 2 CH 3 H H 0 CH 3 0 CH 3 H H H -n-C 6 H 13H H 0 CH 3 0 CH 3 H H &Cl'20- CH3- H H 0 CH 3 0 CH 3 H H &CHOCH 3 H H 0 CH 3 0 CH 3 CH 3 H H PCH 20- CH 3H H 0 CH30 CH 3 cl H H p CH 2 0- CH 3H H 0 CH 3 0 CH 3 CH 3 H H CF 3 CH 2 CF 3 CH 2- H H 0 CH 3 0 CH 3 H H CH 3-W 3 CHFU 2- H H 0 CH 3 0 CH 3 H H CH 3- H.BrF= 2- H H 0 CH 3 0 CH 3 H H CH 3- HUF= 2- H H 0 CH 3 0 CH 3 H H CH 3 - HU 2 W 2- H H 0 CH 3 0 CH 3 H H CH 3 - HW 2 cr 2- H H 0 CH 3 0 CH 3 0 H H CH 3 - HW 2 CF 2-H H 0 CH 3 CH 3 HH-W 2 W 2 H CH 3 HH0CH 3 0CH 3 0 67 GB 2 057 429 A 67 Table IV (continued) RI R R R R R X y 1 1 2 3 4 5 W 1 1 m. p (C) 0 1' H 4-NHCOCH 3 CH 3 CH 3 H H 0 CH 3 0 CH 3 0 H 4-NHCO-i-C 3 H 7 CH 3 H H H H CH 3 H H 0 CH 3 0 -CH 2 CECH CH 3 H H 0 CH 3 0 C(CH 3)2 C2CH CH 3 H H 0CH 3 0 CH 3 CH 3 CH 3 H H -CH ---11 CH H H0 CH 0 CH 2 3 3 3 H H -CH 2-0 CH 3 H H 0 CH 3 0CH 3 68 GB 2 057 429 A 68 Table IV-a so 2 A X R,' W N 3 so 2-C-:N 0 yl R 1 R4 p.5 N -N R,' R1 % 'S W X, Y, m.p. CC) W 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0- H H H H 0 CISO CH 3 CF 3 CH 2 0- H H H H 0 CH 3 CH 3 0- H H H H 0 CH 3 0 CH 3 0 0- H H H H 0 CH 3 0 CH 3 0- H H H H 0 CH 3 CH 3 Ccl 3 CH 2- H H H H 0 CH 3 0 CH 3 0 Ccl 3 CH 2 0- H H H H 0 CH 3 0 CH 3 Ccl 3 CR 2 0- H H H H 0 CH 3 CH 3 CBr 3 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 HU 2 cr 2 CR 2 0- H H H H 0 CH 3 0 CH 3 0 H H 0 CH 0 CH 0 W 3 W 3 CH 2 0- H H 3 3 CF 3 (W 2) 2 CH 2 0- H H H H 0 CH 3 0 CH 3 0 CF 00- H H H H 0 CH 3 0 CH 3 0 CH 3 (W 3)2 CHO- H H H H 0 CH 3 0 CH 3 0 (cr 3)2 CHO- H H H H 0 CH 3 0 CH 3 (cr P2 CHO- H H H H 0 CH 3 CH 3 cl-& 0- H H H H 0 CH 3 0 CH 3 0 69 GB 2 057 429 A 69 Table iv-a (continued) A R,' R 1 CH, & o- H H CH 3 o-& o- H ll 0 2 r; -.& o- H H R4 RS W X y m. P. (c) H H 0 CH 3 0 CH 3 0 H a 0 CH 3 0 CH 3 0 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-Cl H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-CF 3 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-CH 3 0 H H 0 CH 3 0 CH 3 0 cr 3 CH 2 0 H 4NO 2 H H 0 CH 3 0 CH 3 0 CF 3 CH 2 0 H 4-W H H 0 CH 3 0 CH 3 0 U 3 CH 2 0 H 4-F H H 0 CH3 0 CH 3 0 CF 3 CH 2 0 H 4-CH 3 H H 0 CH 3 0 CH 3 0 GB 2 057 429 A 70 Table V so 2 A R# 3 -0 c so 2 N=C=W R 1 9N=C=W R1 R A W (CM-1) H H -N(CH 3)2 0 2220 H H -N(C 2 H 5 1 2 0 2210 H H -N-C H 0 1 2 5 CH 3 H H -N-i-C 3 H 7 0 1 CH 3 H H N-n-C 4 H 9 0 1 CH 3 H H -N-n-C 3 H 7 0 CH, H H -NC] 0 H H -N-CF 2 CF 2 H 0 2230 CH3 H H -N(CF 2 W 2 H) 2 0 H 4-Cl -N(CH 3)2 0 2250 H 4-W 3 -N(CH 3)2 0 2220 H 4-CH 3 0- -N(CH 3)2 0 2230 H 4-F-N(CH 3)2 0 2250 H 4-CH 3 - -N(CH 3)2 0 2240 H 4-NO 2 - -N(CH 3)2 0 H 4-Br- -N(CH 3) 2 0 2280 H 4-C 2 H 5 0- -N(CH 3)2 0 2250 71 k GB 2 057 429 A 71 Table V (continued) VN=C-W RI R 1 A W (CM-1) H 4-CN -N(CH 3 2 0 H 4-(CH 3) 2 N -N(CH 3 2 0 H 4-SCH 3 -N(CH 3 2 0 H 4-SO 2 CH 3 -N(CH 3 2 0 H H -N(CH 3 2 5 5-CH 3 4-CH 3 -N(CH 3 2- 0 5-CH 3 0 4-CH 3 0 -N(CH 3 2 0 5-F 4-Cl -N(CH 3 2 0 5-cl 4-Cl -N(CH 3 2 0 H 3-Cl N(CH 3 2 0 H 5-cl -N(CH 3 2 0 H 6-Cl -N(CH 3 2 0 H H -NCH CN 0 1 2 CH 3 H H -N-CH 2 co 2 CH 3 0 CH 3 H H -N-CH 0 1 2 CHI H H - OCH 2-(D 0 CH 3.

H H -0 --G) 0 H H -OCH 2 W 3 0 72 GB 2 057 429 A 72 Table V (continued) -JN=C-W Ri R 1 A W (CM-1) 0 H 4-CCH 3 -N(CH 3)2 0 0 H 4-c-l-C 3 H 7 -N(CH 3)2 0 H 4-CH 2 OCH 3 -N(CH 3)2 0 H 4-CH 3 0-i-C 3 H 7 -N(CH 3)2 0 H H N-CH CECH 0 9 2 CH 3 H H N-C(CH CE-CH 0 1 3 2 CH 3 H 4-CH 2 SCH 3 N(CH 3)2 0 H 4-CH2 so 2 CH 3 N(CH 3)2 0 H 4-CH SCH N(CH 0 211 3 3 2 0 H H N 0 9 CH 3 H H N-CH 0 1 2 CH 3 z 73 GB 2 057 429 A 73 Formulations Useful formulations of the compounds of Formula 1 can be prepared in conventional ways. They include dusts, granules, pellets, suspensions, emulsions, wettable powders, emulsiflable concentrates and the like. Many of them can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength 5 compositions are used primarily as concentrates which are to be diluted prior to ultimate use. The formulations, broadly, contain about 0. 1 % to 99% by weight of active ingredient(s) and at least one of a) about 0. 1 % to 20% surfactant(s) and b) about 1 % to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the approximate proportions set forth in Table VI.

TABLE VI

Weight Percent Active Ingredient Diluent(s) Surfactant(s) Wettable Powders Oil Suspensions, Emulsions (including Emulsifiable Concentrates 20-90 0-74 1-10 5-50 40-95 0-15 Aqueous Suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 0.1-95 5-99.9. 0-15.

High Strength Compositions 90-99 - 0-10 0-2 Active Ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.

Lower or higher levels of active ingredient can be present, depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, a.nd are achieved by incorporation into the formulation, or by tank mixing.

Some typical solid diluents are described in Watkins, et al., -Handbook of Insecticide Dust Diluents and Carriers-, 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are pr-ferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, -Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0. 1 % is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at O'C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, 20 -Encyclopedia of Surface Activ- Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending, and usually grinding, as in a 25 hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S.

Patent 3,060,084). Granules and pellets can be made by spraying the active material on preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration-, Chemical Engineering, December 4, 1967, pp. 147ff. and -Perry's Chernical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,36 1, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Patent 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164,166,167 and 169-182.

H. Gysin and E. Knusli, U.S. Patent 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4.

G. C. Klingman,---WeedControl as a Science-, John Willey & Sons, Inc., NewYork, 1961, pp.

81-96.

35.

74 GB 2 057 429 A 74 J. D. Fryer and S. A. Evans,---WeedControl Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 10 1 -103.

Unless indicated otherwise, all parts are by weight in the following examples.

EXAMPLE 41 5 Wettable Powder N'-[(4,6-Dimethoxypyrimidin-2-yl)aminoca rbonyll-N,N-di methyl- 1 2- benzenedisuffonamide dioctyl sodium sulfosuccinate sodium ligninsulfonate Synthetic fine silica 90% 0.1% 1% 8.9% The ingredients are blended and ground in a hammer mill to produce particles almost all of which -99% are below 100 microns in size. The product is sifted through a U.S.S. No. 50 screen and packaged.

EXAMPLE 42

Granule wettable powder of Example 41 attapulgite granules (U.S.S. #20-40; 0.84-0. 42 mm) 10% 90% A slurry of wettable powder containing 50% solids is sprayed on the surface of attapulgite 20 granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE 43 Wettable powder N'-[(4,6-Dimethoxy-1,3,5-triazin-2yi)aminocarbonyll-N,N-dimethyi-1,2-benzene- 25 disuffonamide 40% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54% 30 The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

EXAMPLE 44

3 5 Granule wettable powder of Example 43 gypsum potassium sulfate 25% 64% The ingredients are blended in a rotating mixer and water sprayed onto the tumbling mixture to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 mm (U.S.S.#18-40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to 40 produce additional material in the desired range. These granules contain 10% active ingredient.

EXAMPLE 45 Wettable Powder N'-[(4-Methoxy-6-methylpyrimidin-2-yi)amino- ca rbonyll-N, N-d i methyl- 1 2-benzene- 45 disulfonamide 80% GB 2 057 429 A 75 Wettable Powder - continued sodium alkyInaphthalenesulfonate sodium ligninsulfonate synthetic amorphous silica 2% 2% 3% 13% kaolinite The ingredients are blended and coarsely ground in a hammer mill to produce particles essentially all below 100 microns in size. The material is then reblended, sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

EXAMPLE 46 10 Wettable Powder N'-[(4,6-Dimethoxypyrimidin-2-yi)aminoca rbonyll-N, N-d i methyl- 1,2- benze ne disulfonamide 65% dodecylphenol polyethylene glycol ether 2% sodium ligninsulfonate 4% sodium silicoaluminate 6% 23% montmorillonite (calcined) The ingredients are thoroughly blended. The liquid surfactant is added by spraying onto the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 microns, the material is reblended, sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and.20 packaged.

EXAMPLE 47 Wettable Powder N'-[(4,6-Dimethoxy- 1,3,5-triazin-2-yi)a mi noca rbonyll-N, N-di methyl- 1,2benzenedisulfonamide 50% 2% 2% sodium alkyinaphthalenesuifonate low viscosity methyl cellulose diatomaceous earth 46% The ingredients are blended, coarsely hammer milled and then air milled to produce particles of 30 active essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE 48 Oil Suspension N'-[(4-Methoxy-6-methylpyrimidin-2-yi)am inoca rbonyll-N,N-d i methyl- 1 2-benzene disulfonamide 25% 5% polyoxyethylene sorbitol hexaoleate highly aliphatic hydrocarbon oil 70% The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting suspension maybe applied directly, but preferably after being 40 extended with oils or emulsified in water.

EXAMPLE 49 Aqueous Suspension N'-[(4,6-Dimethoxypyrmindin-2-yi)aminoca rbonyll-N, N-d i methyl- 1, 2benzenedisulfonamide 25% 76 GB 2 057 429 A 76 Aqueous Suspension - continued hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5% 5 The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns, and then packaged.

EXAMPLE 50 Extruded Pellet N'-[(4,6-Dimethoxy-1,3,5-triazin-2-yi)aminoca rbonyll-N, N-d i methyl- 1,2-benzene disulfonamide 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkyInaphthalenesulfonate 1 % 15 calcium/magnesium bentonite 59% The ingredients are blended, hammer milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried Oellets may be crushed to pass a U.S.S. No.

20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) maybe 20 packaged for use and the fines recycled.

EXAMPLE 51 Solution N'-[(4-Methoxy-6-methylpyrimidin-2-yi)amino- ca rbonyll-N,N-d i methyl- 1 2-benzene- 25 disuffonamide 5% dimethy[formamide 95% The ingredients are combined and stirred to produce a solution, which can be used for low volume applications.

Utility 30 The compounds of the present invention are highly active herbicides. They have utility for broad spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highway and railroad structures. Alternatively, some of the subject compounds are useful for the selective pre- or post-emergence weed control in crops, such as corn, 35 wheat and rice. By properly selecting rate and time of application, compounds of this invention may be used also to modify plant growth beneficially.

The -precise amount of the compound of Formula 1 to be used in any given situation will vary according to the particular end result desired, including their use as selective or general herbicides, the crop species involved, the amount of foliage present, the species of weeds to be controlled, the soil 40 type, the fornfulation and mode of application, weather conditions, etc. Since so many variables play a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of this invention are used at levels of about 0.001 to 10 kg/ha with a preferred range of 0.03 to 5 kg/ha. In general, the higher rates of application from within this range will be selected for adverse conditions, where extended persistence in soil is desired, or for non-selective weed control purposes.

The compounds of Formula i may be combined with other herbicides and are particularly useful in combination with substituted urea herbicides such as 3-(3,4- dichforophenyi)-1,1-dimethyi urea; the triazines such as 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine: the Ouracils such as 5-bromo-3 sec-butyi-6-methyl-uracil; W(phosphonomethyl)glycine; 3-cyclohexylA - methyl-6-dimethylamino-s- 50 triazine-2,40 H,3H)-dio-ne; N,N-dimethy]-2,2-diphenylacetamide; 2,4- dichlorophenoxyacetic acid (and closely related compounds; 4ch loro-2-butyny]-3-chlorophenylca rba mate; diisopropylthiolcarbamic 77 GB 2 057 429 A 77 acid; ester with 2,3-dichloro-allyl alcohol, diisopropylthiolcarbamic acid, S-(2,3,3-trichforoaiiyi)ester; ethyi-N-benzoyi-N-(3,4-dichforophenyi)-2-aminopropionate; 1,2-dimethyi-3, 5-diphenyi-pyrazolium methyisulfate; methyl 2-[4-(2,4-dichforophenoxy)-phenoxylpropanoate;4- amino-6-tert-butyi-3(methyithio)-1,2,4-triazin-5(4H)-one; 3-(3,4-dichlorophenyi)-1 -methoxy-1 -methylurea; 3-isopropyi-l H 2,1,3-benzothiodiazin-(4)-3H-one-2,2-dioxide; a,a,a-trifluoro-2,6-dinitro- N,N-dipropyi-p-toluidine; 1,1'-dimethyl-4,4'-bipyridinium ion; monosodium methane-arsonate; 2chloro-2',6' diethyi(methoxymethyi)acetanifide; and 1,1 -dimethyi-3(a,a,a-trifluoro-m- toiyi)-urea.

The activity of these compounds was discovered in greenhouse tests. The tests are described and the data resulting from them are shown below.

TEST PROCEDURE A Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgallil, wild oats (Avena fatua), cassfa Wassia tora), morningglory (Ipomoea spp.), cocklebur (Xanthium spp. ), sorghum, corn, soybean, rice, wheat and nutsedge tubers (Cyperus rotundus) were planted in a growth medium and treated pre emergence with a nonphytotoxic solvent solution of the compounds. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliate leaf expanding, crabgrass 15 with two leaves, barnyardgrass with two leaves, wild oats with two leaves, cassia with three leaves (including cotyledonary ones), morningglory with four leaves (including the cotyledonary ones), cocklebur with four leaves (including cotyledonary ones), sorghum with four leaves, corn with four leaves, soybean with two cotyledonary leaves, rice with three leaves, wheat with one leaf, and nutsedge with three-five leaves were sprayed with a noriphytotoxic solvent solution of the compounds. Other 20 containers of the above mentioned weeds and crops were treated pre- or post-emergence with the same nonphytotoxic solvent so as to provide a solvent control. A set of untreated control plants was also included for comparison. Pre-emergence and post-emergence treated plants and controls were maintained in a greenhouse for sixteen days, then all treated plants were compared with their,-espective controls and rated visually for response to treatment using the following rating system and symbols. 25 0 = no effect = maximum effect C = chlorosis or necrosis D = defoliation E = emergence inhibition G = growth retardation H = formative effects U = unusual pigmentation 6Y = abscised buds or flowers _i OD bA 00 0 0 cn n x z: w n z n n n: o C 6 c 0 0 f-4 0 0 (D n c4 pd to in 0 m to z 0 td (n m n d bi cn (D ryl td (n 71 V.

o:1 t-4 9.4 L 0 c. h rxi 0 to m 1.4 bi td 0 W 0 ri C) to (A 0 rxi.90.

r- en 0 cn t, 0 0 0 Ub In tn n CIA 0 o 0 a 0 nonnon k^ co co o 'non o X0 0 C-N 0 n n fid C-NIA-C-1111-SO 0.0 1 0 %C=N 2-P 1 CIA 3 0 (elf 3) 2-N-SO 2 ell 3 0 0 0 M 0 W n w m o n n n n n nnnnn o,c /c N to 0 a 0 ko 00 non C.) 0 N C-NII-C-NII-SO n ell 3 (ell 3) 2-N-SO 2 ell 0 XO ko kc > j- XO 'D 0 W n C: L4 nnnnnnon coLn L" r 3 mnnnoinac) cl n 0 -N ko o. 1X. kO ko xo.o a i ko ko 110 n ke lie C-NII-C-NII-SO cl 2 lc=N 1 C11.3 (CH 3) 2-N-SO 2 1 ' v,) 11 1 m N (0 79 GB 2 057 429 A 79 Test A (continued) ywyu 0 z z O:W z kg/ha 0.1 0.1 POST-EMERGENCE BUSEBE.A: -9D, 9G 9D, 9G COTTON gc gc MORNINGGLORY loc loc COCKLEBUR loc gc CASSIA 9c SC, 9G NUTSEDGE 8G 6C, 9G CLABGRASS 9c 9c BARN-iARWRASS 9c loc WILD OATS 9c 9c WHEAT 4C, 8G SC, CORN, loc -9c SOYBEAN 9c 9c RICE 9c gc SORGHUM 9c lue PRE..1M,ERGENCE MORNINGG1ORY 3C, 9H.9 G COCKLEBUR 9H 9H CASSIA 2C, 9G 3c, 9(i NTUTSEDGE 9 lu CRABGRASS 10E 4C,.4ki BARNYARDGRASS 2C, 9H 5c, 9R WILD OATS 2C, 9G.3c ' E4G WHEAT 9H vn CORIN lc,9G 5ki OYBEAN H- 9R RICE 10E luL 10H loH M ún 0 b4 to n "I to n X 'd c^ W G1 p m bi n,;o. n n x n to 10 6 0 Pd Ub > PO (A W 8 o w 0 m o z b.4! c t- o C) (-- o:r K:0 > tl b4 X! m m R t ' to _4 rts d #-I to t^ to 0 to t4,1 ell 0-4 n C. to U % (n 1,1 d %e 0 lit U% 0:d g. t,l en 'I tl 0 s z ewe (n n n -09 t- U), 0 c) to X0 ko W nx.,n f- r m n eW W E- I- W W cnnc)onnnanc>nnn C> ell M n n co ko W n nn n 0 3 to so 2NII-C Nit-xoN o, CAR 3 cli so 2N \ell 3 ,0 kD F f-0 co p bj 'D co W ko a [- ko 0 pj ko kD ko,,J Ln a o n n a n Pi G) 1. til 1 nnno 1 1 nnannnnan C) OCII 1 3 co co -1 10 ul co 1., 1 0 n n o N Z! 1 S02MI-:-NW(O 11 zo N --( c 11 5 0C113 SO Nl.

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4n C) n,c) c nnnnn tn l- tn ' non N b W ti ul tn W W 1 Lq o C1 cl 0 OCII C1 trj. C-Onnnnnnnn z; 3 to NI kc kc to ko 00 ko 7 00 ko ko -j M ko zo Z0 Z0 D o 0 SO NII-C-Nif - kD 2 M tn n (n W. o o n n n n 5 N C11 3 so 2 N (M 3)2 hi b3 nncoon W bj M W C) 0 ch W W ko Ocil n n m 0 ' tTI 1 n n 1 nnnnnona 110 n 3 00 kD kD W S02N11-,C-NII OCII 3 S02OCII2CP3 'I l) M A.

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to pi r, 5o (7) 4 c^ re u e-1 U p 5. 1,1 (a 7, 'It:l:

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W - CO ko ti koo I- ko W W c) p pir. n c tyl ko 0 G) 0 n:

C. to n Z U to I^ M ti n -3 U) m ko ko ko to ko K) K) ui t.

nnnono ko %ko ko 'W zo n 0 n to cl (n n d PC n to 0 eQ 0 0 C. tn o ul :t to 4 0 n t_ n ko ko ko 0 0 ocil 3 (X so 2 Nil-C-NII- 0 N C11 3 C11 3 so 2 N 0 N I so 2 NII-C-NW( 0 N SO N C11 3 2 c 2 11 5 OCII 1 orll 3 bl G) m N 0 (n -4 -PN (D co j OD OD 1 a'[-. U) C-4 ---i 4 n z n z 'd n z n m n 7q n 0 C z m 0 0 = n 1- n) m as 0 c A. 0 c: 0 a: -,Q - m 0 1- 0 03 M (D -1. W i,[U U) 1 rt f. n () (0 cl M M - m h-:3F, _ m 1,1 gu gu (D cr (n 4:9 (J):i rt (a 2 C?:J m %U:j:3 a. 0Q:1 0, rt (t) 0 (0 (D P. P. 0 fD (D Cb cl r? a' n M. to X OQ PA J (D rib 91. (D FD tl 0 N 1 U) 0 0 c 0 m &-- iQ CL cr CL. 0 11 c 14 UQ 0 m mi m (D (D (D c: to a) (D 0 0Q rt a (n:Y (D IQ A m (n (tQ tn CL 0 tn tn ti a) m M U) (n jj. (n (0 tn 3 W -3 m 00 W n o:z n c> c) n n 0 m c) 0 c) n m c) 0 0 n o cp n C) N 0 I n- - nn. m n- - in n 5. - - m n. 00 oo XX j 00 co 00 00 00 %D CN X0 HIC nn n 0 nn n no n -Nif-C-Nill-so 2-C C-N 00 1,) 1- a on i_ I- a i,- M:) cl] 0 (ell 3) 2-N-50 2 0 0 n n 0 c> n n n c 0 0000c- D 0 0 n ci, n - F- c 3 0 c m-. n n m m n 0 n C) CY n -. M n n C0 co ko 00 kD ko a% n n elf 0 I_ co ( i _ 00 t_n 00 00 a, F- 00 1- 1-1 I_ a% I- ko 4.1 XD 3 X nonnonnnnnonooor)cDnnnn p n C-N 0 . n. --4.. m n n nn- r11 n. c) 00 cr) M 00 OD ko ko kit ko m N -Nil-(,-Nif-SO 2 C -N G -A F00 M 00 XD 1- 1- 1- m ko 00 X0 1 o n n 6 n n C') m mnnnn C11 0 (ell) N-SO n. - 3 0% 00 00 _A ko kD n n r') 3 2- 2 tD a j 'O IH (D In Irt td a) CV m 0 (n i _Ph N CD 00 00 89 GB 2 057 429 A 89 Test B (continued) 9 0 CH 0 3 N 0 \k to HR C-NH-C-ITH-SO 2- 1 C -N CH 3 (CH 3)2-N-SO 2 1 Rate,kalha 0.008 0.03 0.06 0. 25 3H. 7G 7C. 9G lor loc loc loc loc loc loc loc 10E 10E 5C. 7G 8C, 9G 6G 9C, 9G loc loc 7C, 8G 6C, 8G 1Qc 5H, 7G 9G 8G 4C. 8G SC, 6G SC, 7G 3G 3C, 7G Crabgrass Barnvarderass SorRhum. Wild Oats Johnsongrass Dallisgrass Giant Foxtail Ky. bluegrass Cheatgrass Sugarbeets Corn bfu-s c a rd Cocklebur Pigweed Nutsedge_ Cotton Morningglory Cassia Teaweed Velvetleaf Jimsonweed Soybean Rice Wheat 8C, 7 9C, 9G SH, 9G loc loc loc loc loc loc 7H, 8G 8C,6G 9C.7G 9C, 9G 7C, 9G loc loc 10E 8C, 9G loc loc 8G 10E 8E, 9G 3H. 7G sc, 8G 6C, 8G 9C. 8G 9C. 8G 6C, 8G 3C, 8G 10E 8C. 8G lOC loc loc loc 10E loc loc loc 3C, 8G 10E 10E SC, 9G loc 7C, 8G 9C.8G loc 8C.8G 8C, 8G 10E loc 10E 6C. 8G 10E 8G loc sclei loc loc 7C, 8G 10E loc 1 GB 2 057 429 A 90 Test B (continued) 1 CH 3 NH-C-NH 2 SO N -CH3 2 \ c H CH 3 Rate kglha 0.03 0.12 4G 7G 7C.IC 8G,6C Sorzhum loc Wild Oats 6C.4C Johnsonerass -'RH 8G.5e Giant foxtail 6G,3C loc Kv. blueerass 7G,3C 8G,6C Cheaterass 8G3C 9G.9C Suearbeets 6G.4C 8G,6C Corn 6G.SH 8G,SU Mustard 8G,9C 9G,9C Cocklebur 6G.SH 7G,5H Nutsedze 8G 9G Cotton 8G 8G Mornine or 8G 8G,4C Cassia 5G 8G,7C Teaweed 3C 8C Velvetleaf SG,5C 7C.7C Jimsonweed SQ,6C 8G.9c Sovbean 0 2G,1C Rice 10E lOE Wheat SG4C 7G,5C 1 A 4 r 1 50 NH-C-Nii 2SO N 1,01 CH 3 2 \ c 2 H 5 CH 91 GB 2 057 429 A 91 Test B (continued) OCH12 Rate kglha 0.03 0.12 7r. 2e 8G. 4C 7C. 8C.7C 1 or_ loc Sorehum Wild Oats Johnsonerass SG,3C 6G,3C 7G,5H 8G sc Giant foxtail 8G.3C 9G.8c Kv. blueRrass Cheatzrass Su%arbeets Corn Mustard Cocklebur Nutsedee Cotton Morningglory Cassia leaweed Velvetleaf Jimsonweed Sovbcan Rice Wheat 7G 7G. 7C 7G, SC 6G, 5H 9G. 9C 8G. SH 7G 5G 8G, 3C 4G 3C 4G. SC 6.G. 6C 1 C 7G. 7C SG, 2C 7G. 4C 10E 7G, SC 7G: 3H loc 8G. SH 5G sc 8G. I&C 8G.7C 92 GB 2 057 429 A 92 Test B (continued) 0 OCR 3 so 2-NH-C-NH CH 3 so 2 N c H OCR 3 RAte kgl.ba 0.03 0.12 -Cral-cr:xcc 6G,2C 8G,3C RzrnszrA&-goc 7G.2C 8G,5C Sorchum 10C 10E Wild Oats RG,3C 5G,3C Johnsonerass 8G,3H 8G,5H Giant foxtail 6C.3C loc Ky. bluetrass 7G 8G,5C Cheaterass 7G.3C 8G,8C Sui 4C. 8G,6C zarbeets 6G Corn SG,3H 7G,5H Mustard 9G.9C lOC Cocklebur 5G 7G Ir NutsedRe 9G 9G Cotton 5G 8G MorningglorX 7G,5C 8G,-5c Cassia 6G 8G,8C Teaweed 0 4C Velvetleaf 4G.3H 7G,6C jl,nscnweed 6G.SC SG,5C Sovbean 0 2G Rice 10E 10E %"n e a t 4G,2C SG.3C TEST PROCEDURE C Twenty-five cm diameter plastic pots filled with Fallsington silt loam were planted to soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutflon theophrastil, sesbania (Sesbania exaltata), Cassia (Cassia tora), morningglory (tpomoea hederacea), jimsonweed (Datura stramonium), 5 cocklebur Wan-thium pennsylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus rotundus), bamyardgrass.(Echinochloa crusgalli),"giant foxtail (Setaria faberfil and wild oats (A vena fatua).

Approximately 2-1/2 weeks after planting, the young plants and the soil around them were sprayed overall with the test chemicals dissolved in a non-phytotoxic solvent. Fourteen days after treatment, all species were compared to untreated controls and visually rated for response to treatment. The rating 10 system was as described previously for test A. The data are presented in Test C. It is obvious that some of the compounds have utility for selective weed control in crops such as wheat and rice.

K co W 0 M- M. P1 0 0 M- E- 0 0 ab ib (D 0 m h- n 0 M n 9 h% cl rt m 0 1< 3Q p. 0 m:J (D cr 0 X to gu:3 rt m a..4 a.

re rt 0 0Q h- 0 o m. fu m m bl 0.

tl fD 2 " 0:3 re rt 0 X OQ UQ 0 1 PO 1 1- D XO to 00 ko b- PP. n PD n nP' c- 0 0 0 c 1 . m o _ b4 3% 0 0 0000000 0 C c -H ON m n n n n n n o a o p o 0 0 0 C) Z) n 0 _.... nnnnc-innnn-)- h- t- - _ (Cif c:-0 0 0 0 elf 0 3 2-N-So 2 3 F_ 00 0 onnnnnnnonnoaon Cif 0 n. nnn. nn o 3 o 0 0 0% 0 0 C) 0 0 c 0 -N N117C-NII-SO 00 bj ko 2 CN co F- nn. Mnnn. n n 1.1 (CIA) -N-SO CDC> oc)no 0 Itno 1 TC cif 0 32 2 n 3 00 10 tlj 0% W c o F- <D CIA 0 nnnn- n.. 6 3\ 0 0 0 C) $.- at -N n n n n n,x Ile, C-NII-C-NII-So - 1 2 C -N co n n c:) cD n (ell nnnn nn ell 3 2-H-So 2 1,011 3 a C) 0 CD c n CD 0 onnn 1 In n n 0.3 (D cb c n G) co 1 N (D W 94 GB 2 057 429 A 94 Test C (continued) CF3 0 2 1) 502NH-C-Nti. C S02 N(CH 3)2 Rate kglha 0.25 0.12 0.06 0.03 Sovbeans 1OG,8C IOC 11OG,6 10C loc Velvetleaf loc loc lloc loc loc Sesbania 1OG,9C loc lloc loc Cassia 1OG.9CilOC IJOC loc 110c,9C Cotton loc 1OG,7C, 1OG.9C1OG,SCI9G,3C Morningglory 10C SCiloc loc 10C 1OGAC Alfalfa lOC IQG-7C]-IC 8e Jimsonweed I- 10C.7C 1 - - Cocklebur 1OG.9 EE n 1OG.9 1OG.7C Corn 2Q.1e le 0 0 Craberass 9G 0 2G 0 - Rice 6G.1C 4G 2G _n Xutsedee 8c. lc 1 9c 5G 1 gr- 7G Barnvardprass - 18G.2C 4 r, 5c, IG Wheat 7G.1C 1 5G 0 2G IG Giant Foxtail 2G 1- 0 - Wild Oats 1G ISG,1C 1 0 0 0 Sor2hum 7G.2C 8G.3C 9G,2C 4G,1C4G OCH OCH 10.003 SG, 7C loc 0.013 0.007 11OG, 7C lor 10MC 9C.4C loc 9G. 3C sc 7G. 3r-SC. 6 rlO-5G. 1 C 1 (6G 7 r, - 0 1G 2G, IC 9G. SC 9G. 4C 9c 7G. 2C - 1 n 0 0 7Q ') C0 2G 2G, IC 1 GB 2 057 429 A 95 Test C (continued) cl 0 OCH 3 9 N so 2 NH-C-NH-k NC.

k CH 3 so 2 N(CH 3)2 0.25 0.06 10MC 1OG 4C 9e 9c 9c loc 10c116c 1OG.7C 10GAC 1OG,7C 1OGAC 1OG 8C Sc SC gc 1OG.6C 4G,1C 1G 4G 5G 8G,2C 8G,2C 7G 7G 7G.2C 5G gGlic 8G 8G 2C 3G 8Q.2C 9G.3C Rate JTlha 0.015 So,vb eans_ Velvetleaf Sesbania Cassia Cotton Morningglory Alfalfa Jimsonweed Cocklebur Corn Crabgrass Rice Nutsedge Barnyatdgrass Wheat Giant Foxtail Wild Oats Sorghun 1OG. 3C 8E, 4C 8c 1OG, 5C 1OG, 7C 1OG, 7C 8C 9G, Z-C0 4G 6G. 1C SG, 1C 96 GB 2 057 429 A 96 Test C (continued) 0 OCH S02NH-C-NH-11 OCH 3 so 2 OCH 2 cr 3 RAte kalha 0.12 0.06 0.03 0.015 Soybeans 1OG,8C 1OG.6C 8G,6C 8G.5C velvetleaf 9G.6C 3GI2C Seshania 1OG.7C 7G,3G Cassia 1PC i0G.5c 1OGI6C 7G.3CJ Cotton 8G3C 9d26C lc Mornineglory - 1OG4C 7G,3C Alfalfa 9G.6C 9G,3C 9GI6C SG,2C Jimsonweed 0 3G 0 Cocklebur 9G,3C 1OG,6C 1OG.7C 9G,2C Corn 0 2G IG 0 Crabgrass 4G,3C lc 4C 1G Rice 7G.2C 3Gz1C 0 Nutsedge 9G 9G 8G,1C 5G Barnvardgrass 9G92C 7G,2C 8G 2C 1G W-heat 0 0 0 0 Giant Foxtail -- - Wild Oats 2G 0 1G 0 Sorghum 6G.2C 7G.2C 6G.2C 2G 1; 97 GB 2 057 429 A 97 Test C(continued) 0 OCH 3 so 2 NH-C-NH-(C,,N N -( OCH 3 so 2 OCH 2 CF 3 RAte A-clha 0.12 0.06 0.03, 0.015 So.vbeans 9G,6C 1OG,7C SG,4H SG.SC Velvetleaf 1 9G,6H 6G,3C Sesbania 8G,4C SG,3C Cassia 9G,5C 8G ' 3C 9G,5C 7G.3C Cotton JOG,4C 8G.3C 9,G-,3-C-. 4G.3C Mornineglory 1OG.8C 8G,3C 9G,6C Alfalfa 9G,6C 3G 8G, 4C 0 Jimsonweed 5G 0 Cocklebur 1OG,8C 1OG,6C 1OG,8C!OG-, 4C Corn 7G,2C 9G,3C 6G,1C G H 11:7-G Crabgrass 1OG'SC 8G 1OG,3C Rice 0 6G,1C 2G Nutsedge 6G 3G 6G 0 Ba,rnya-.dgrass 6G 7G 5G 5G X 'h e a t 0 0 0 0 Giant Foxtail - - - - Wild Oats 1G 3G 0 1G Sonhum 8G.3C 9G,3 9G4C 4G,1C 98 GB 2 057 429 A 98 Test C (continued) OCH 3 N S02 NH-C-NH-IX N C3 so 2 OCH 2 CF 3 0.12 0.06 0.03 0.015 Soybeans 9G,4C 9G.SC 8G.SC 8G,4C Velvetleaf 9G.SC 4G3C Sesbania 7G4C 3G.2C Cassia 9G 3C 8G4C 6G.2C Cotton 10C 8G,3C 9G,Sc 6G.3C Morninzslorv 9G4C 10MC 9G4C 1OG,4C Alfalfa _ 1OG,7C 9G,3C 1OG97C 7G.2C Jimsonweed 6G 2G Cocklebur 1OG,8C 9G,4C 9G.6C 9GAH Corn 3G 5G 1G 2G Crabgrass 9G.4C 7G,1C SG,3C SG,2C Rice 4G,1C SG,1C 4G,1C 4G.1C Nutsedge 7G.3C 9G,2C 5-G-JC 7GAC Barnyar:dgrass 9G,2C 8G 8G.1c 7G Wheat 1G 0 1G 0 Giant Foxtail Wild Oats 1G 7G,1C IG 5G SorRhum 9G.2C 1QQ3C 9G.2C 9G.3C k 99 GB 2 057 429 A 99 Test C (continued) 0 OCR f so 2 NH-C-NH 0 N W CH 3 so 2 OCR 2 W 3 Rate k-71ha 0.12 0.06 Soybeans 1OG.3H 1OG,7C Velvetleaf 9G,5C Sesbania 9Q.4C Cassia 1OG,8C 7G.3C Cotton 9G.6C 8G4C Morningglory 9G4C 1OG,8C Alfalfa 1OG,7C 9G.3C Jimscnweed 7G,1C Cocklebur 1OG,8C 1OG 7C Corn 8G.2C 8G,2C Cr-abgrass 1OG,4C 3G,1C Rice 2G,1C 4GI2C Nutsedge 4G 0 Barnvardgrass 2G.1C Wheat 0 0 Giant Foxtail - - Wild Cats SG.3C 2G Sorehum 9G.2C 0.03 9C. 3H - 1 10G. 7C 7G.3C 1OG, SC 8G. 6C 8G. 2C 1OGI4C 0 2G 6G 0 5G. 3C 0 10C. 2C 8G. 2C 0.015 8G, SC 8G.3C 7G, 3C 7C,3C 6G,3C 1OG.7C 7G, 2C 5G 9C, 4C 7G, 2C 1G, 1C 3C, 1C 0 1G 0 GB 2 057 429 A 100 TEST PROCEDURE D Purple nutsedge (Cyperus rotundus) tubers were planted about 2 cm deep in Fallsington silt foam soil contained in 10 cm diameter plastic pots. Five tubers were planted in each pot. Compounds of this invention were dissolved in an non-phytotoxic diluent and sprayed at 560 1/ha in four methods of application: soil surface, tuber/soil, soil incorporated, and postemergence. The soil surface spray consisted of spraying the compound on the surface of the firmed covering soil. The tuber/soil spray consisted of spraying the compound on exposed tubers and subtending soil before adding the untreated covering soil. Soil incorporated treatment consisted in mixing the compound with the covering soil before using it to cover the tubers. The post-emergence treatment was sprayed on nutsedge foliage and the surrounding soil surface when nutsedge had emerged and grown to a height of about 12 cm. Pots 10 receiving the post-emergence treatments were placed directly in the greenhouse. Pots receiving the other treatmentswere misted with about 0.3 cm water before being transferred to the greenhouse. Response ratings assessed after four weeks are recorded in Test D, based on the same rating system as described in procedure A.

t k Y 101 GB 2 057 429 A 101 Test D Nutsedge Control Compound @em c z % if C Response Ratings (After 4 Weeks) Pre Emergence Rate Soil kg/ha Surface 0.008 8G 0.03 9E,9G 0.12 10E 0.008 7G 0.03 2C,7G 0.12 8G 0.008 2C,6G 0.03 9G 0.12 10E Tuber Soray SC, 8G 10E 10E Soil Incorp.

PostEmergenci SE, 8G 10E 10E 5C, 6G 8C, 1OG lOC 1 C4 0 rn C ri W U 7G 2C, 7G 2C, 8G 8G SE, 9G 10E 7G 2G 2C, 7G 3C, 5G 2C, 8G 3C, 3G SE, 8G C4 W 9E, 9G 10E I 4G 3C, 5G 1 1 9C 1 1 102 GB 2 057 429 A 102 TEST PROCEDURE E Twenty-five cm diameter plastic pots filled with Fallsington silt loam were planted with corn (Zea mays), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloa crussgallil, johnsongrass (Sorghum halepense), sorghum (Sorghum vulgare), crabgrass (Digitaria sanguinalis), cassia (Cassia tora), 5, cocklebur (Xanthium pennsylvanicum), morningglory (Ipomoea hederacea), field bindweed (Convolvulus arvensis), jimsonweed(Datura stramonium) and velvetleaf (Abutilon theophrasti). Approximately 2-11/2 weeks after planting, the young plants and the soil around them were sprayed overall with the test chemicals dissolved in a non-phytotoxic solvent. Fourteen days after treatment, all species were compared to untreated controls and visually rated for response to treatment. The rating system was as described previously forTest A. The data are presented in Test E. It is obvious that these compounds 10 have utility for selective weed control in corn.

Test E OVER-THE-TOP SOIL/FOLIAGE TFEATMENTS cr 3 0 N 0 so 2-NH-C%?-X-H--\/ 0 N so 2 N(CH 3)2 OCH 3 OCHI 0.06 0.12 0.25 0 0 1G 9G 9G 8G 5G, 4C 7G 9G, 2C 7G 10C 10C 10C 10C 10C 10C Rate kglha 0.03 4G, 4C 6G 7G, 3C 3G 10C 1OG,9C 1 0C 10C 10C 10C 4G 6G 7G, 2IC 0 10C 10C 10C 10C 10C. 10C Corn Nutsedge Barnvarcarass Johnsonarass Sorahum Crabarass Cassia CockleSu-r Morningglory Field Bindweed Ji,-sonweed Velvetleaf

0 1OG, 9C 10C 10C 10C 1OG, 6C 10C 1 iwl 103 GB 2 057 429 A 103 Test E (continued) OVER-THE-TOP SOIL/FOLIAGE TREATMENTS 0 N so 2-Mi-C-NH-\1 0 @ N so OCH1W 2 c; 3 OCH 3 OCH 3 R&te kalha 0.03 0.06 0.12 0 0 6G 9G 0 2G 0 4G 0 3G 0 9G-f8C 8GP6C loc 9G,5C loc loc 9G,3C - 0 3G loc loc Corn Nutsedice Barnvardarass Johnsonarass S o r album Crabgrass Cassia Cocklebur Morningglory -Field Bindweed Jimsonweea Velvetleat

0 8G 2G 4G 3G 0 1OG, 7C 9G, 5Y, loc 9G, 2C 0 loc 104 GB 2 057 429 A 104 Test E (continued) OVER-THE-TOP SOIL/FOLIAGE TPtEATMENTS CH 3 so 2-NH-C-NH- 0 CH SO N 2 5 2 IN, c 2 H 5 c H 3 Rate kglha 0.015 0J03 0.06 0.12 Corn 0 0 Nutsedae 0 5G Barnvardarass 0 0 Johnsongrass cr,-7r RG,1C Sorahun, 8G,1C 9G,1C CraScrass- 0 0 Cas'sla 9G,3C 9G,5C 103,7C 1OG,9C Cockl-eU-ur SG,4C loc 8G,2C loc Mornincalory loc loc loc loc Field Bindweed 9G,3C 1OG'sc 1OG,6C 10C

Jinsonweed 3G 4G 7G 8G Velvetleaz loc loc loc loc -il lc F. 1 GB 2 057 429 A 105

Claims

CLAIMS 1. A compound of the formulae or wherein A is NIR2R3, OCH2CC13, OCH2C13r3 or OCH2CF2Rb or R 1 R1 so 2 -A W so -C-N-R 2 9 6 R 4 R 5 so 2 A S-B N so 2 N=-NH- 0 z (0_ N - X 1 y 1 0 _.g R a OCHR.

1 CF3 1 IA 5 where R. is H, Cl, CH3, OCH.orNO2 and Rb is H, ForCl-C2 alkyi with 0- 5Fand R. is CH.orCF3;10 R1 is H, Cl, Br, F, Cl-C3 alkyl, N02. OCH3, 0 11 C-Rd, CH20Rd, CF3, NH2, N=C=Q 0 0 0 11 11 11 NH-t--hd, imn-[--imrlrld U[ IMP'_k'_Urld where Rd 'S Cl-C3 alkyl, or R, is N(CH3)21 CK CH2SOnCH3 or S(O),,CH,, where n is 0, 1 or 2; 15 R' is H, Cl, F, Br, CH3 or OCH3; R2 is H, C,-C, alkyl, C3-C, alkenyl, C3-C, cycloalkyl, C4-C-, cycloalkylalkyl, Cg-C, cycloalkenyl, C3-C, alkynyi, C3-C, cycloalkyl substituted with 1-2 CH3 groups, CF2CF,H, CF2CHFCI, CF2CHFI3r, CF2CHFCF3, C(CHICN, (CHACK where m is 1 or 2, CH2CH2OCH31 CH2CH(CHJOCH3, (CH2)30CH3, CHR7CO2R. or CHR7 CON(R1, where R. is H or.CH3 and R. is C,-C, alkyl, OCH., 20 119 ' CHR 7--a R or OCHR 7 R 9 where R. is H, CH3, Cl, Br or F; R3 'S Cl-C4 alkyl, C3-C4 alkenyl, CH2CH2OCH3, CH2CH(CH3OCH3, CH2CF31 or (CH2) CN, where m is 1 or 2, or CHR7C02%, 25 NR2R3 taken together are J_\ -N0 or 25.

106 GB 2 057 429 A 106 R4 and R, are independently H or CH3, but R4 and R. cannot both be CH,; R6 is X X N-- N-N - N - I\z N or X N - \ j Y Y Y wherein X is H, CH 31 CH30 or CH3CH,O; Y is Cl, Br, H, C,_C3 alkyl, CF3, NHCH3, N(CHI, OCH,CF,, OCH3, OCK, SCH,, O(CHjPOR,., where p is 2 or 3 and R,, is CH3 or C2H,, CH2CH2OCH3, CH20CH3, CH,OCH2CH3, OCHRICO2R,1, OCHR7 CON(RJ21 C02R11 and CH2C02R11, where R,, is H or Cl-C, alkyl, CH2M, NCi\13(CH2M), CH2CH2M, CH2C1, N3, OCH2CH=CH2 or OCH2C=_CH; X, is H, OCH3 or CH3; Y1 is H, OCH3, OCH2CH3 or CH3, provided that X, and Y1 are not both H simultaneously; Z is N or CH; W is 0 or S; and B is Cl-C, alkyl, CH.CH20CH,, CH2CH2OCH2CH,, CH,CH2CH2OCH,, CH2Q, CH-Q 15 1 Lt'3 where Q'S C02-C,-3 alkyl, 0 CH 0 11 / 3 -CN OCH3 provided that:

0 11 0 1 1 -CN(C1-3a'kyl)2, -k'IMMkt'l-t-3 alKY1),CM21 phenyl, phenyl substituted with chlorine, CK C2-4 alkenyl, C2-4 alkynyl, OR,',, where R,', is C1C alky], -CH20CH2CH2OCH3, or -CH20CH2CH2OCH2CH3; 1) when R2 is OCH3, R3 is CH3; 2) when R, is CF2CHM, CF2CHIFI3r, CF2CF2H or CF2CHI7C173, then R3'S Cl-C, alkyl; and their agriculturally suitable salts.

2. The compounds of Claim 1 wherein R4 = R5 = H.

3. The compounds of Claim 2 wherein W= 0.

4. The compounds of Claim 3 wherein R, = H.

5. The compounds of Claim 4 wherein R 6:Is X N -- \z N = Y

6. The compunds of Claim 5 wherein A is OCH2CF3 or NR2R, and R2 is C,-C, alky], C:-C4 alkenyl, OCH3, CH2CH2OCH3, CH2CH(CHJOCH3 or (CH2)30CH3, or NR2R3 taken together are 30 -N3-NI---\0 or

7. The compounds of Claim 5 wherein R3 '

S C,_C4 alkyl or where NR2R. taken together are I- Pi IC -,t Q 107 GB 2 057 429 A 107 -N] -N 0 1 8. The compounds of Claim 6 wherein R3 IS C,-C4 alkyl or where NR,R3 taken together are -N -N 0 1 or -N / or -N OCH 3 3 CH / OCH 3 \ CH, -

9. The compounds of Claim 8 wherein R, is H, Cl, CF3, N02, CH3 or OCH3.

10. The compounds of Claim 9 wherein R2 is C,-C4 alkyl or NR2R3 taken together are -N3 Or -N 0

11. The compounds of Claim 10 in which X is CH3, OCH, or OCH2CH3; and Y is H, CH3, CH3CH2, OCH,CF3, OCH3, 0C2H, OCH2CH,0CH31 CH,0CH, CH2CH2OCH3, N(CH3)CH,CK OCH2CH=CH2, or OCH2C=_CH.

12. The compounds of Claim 11 in which is CH., OCH3 or OCH2CH3; and is CH3, OCH2CF3, OCH3 or OCH2CH3.

13. WAK6-Di methoxypyri midin-2-y1)a m inoca rbonyll-N,N-di methyl- 1,2benzened isu Ifona m ide; and its agriculturally suitable salts.

14. N'-[(4,6-Dimethoxy-1,3,5triazin-2-yi)aminocarbonyll-N,N-dimethyl-l,2benzenedisulfonamide; and its agriculturally suitable salts. 20

15. N-[(4-Methoxy-6-methylpyrimidin-2yi)aminocarbonyi]-N,N-dimethyi-1,2benzenedisulfonamide; and its agriculturally suitable salts.

16. W-h-Meth oxy-6-methyl- 1,3,5-triazin-2yi) a minoca rbonyll-N,N-di methyl- 1,2benzenedisuifonamide; and its agriculturally suitable salts.

17. W4K6-Di m ethyl- 1,3,5-triazin-2-yi)a m inoca rbonyll-N,N-di methyl- 1,2-benzened isu Ifona mide; and its agriculturally suitable salts.

18. N 14K6-Di methylpyri mid in-2-y1)aminoca rbonyll-N, N-di methyl- 1,2benzened isu Ifona mide; and its agriculturally suitable salts.

19. N'-[(4-Methoxy-6-methylpyrimidin-2-yi)aminocarbonyll-N,N-diethyi-l, 2benzenedisulfonamide; and its agriculturally suitable salts.

20. N-[(4,6-Dimethoxy-1,3,5-triazin-2-yi)aminocarbonyll-N,N-diethyl-1,2benzened isuifonamide; 30 and its agriculturally suitable salts.

21. MAK6-Di methoxypyri midi n-2-y1)a minoca rbonyll-N,N-diethy]- 1,2benzened isu Ifona mide; and its agriculturally suitable salts.

22. W4K6-Di methylpyri mid in-2-y1)aminoca rbonyll-N,N-diethyl- 1,2benzenedisu Ifona m ide; and its agriculturally suitable salts.

23. N'-[(4-Methoxy-6-methyi-1,3,5-triazin-2-yi)aminocarbonyll-N,N-diethyi1,2- benzenedisulfonamide; and its agriculturally suitable salts.

24. W4K6-Di methyl- 1,3,5-triazin-2-yi)a m inoca rbo nyll-N,N-d iethyl- 1, 2-benzenedisu Ifona m ide; and its agriculturally suitable salts.

25. N 2-[(4,6-Dimethoxypyrimidin-2-yi)aminocarbonyll-Nl,N-dimethyi-4(trifluorome thyi)-1,2- 40 benzenesuifonamide; and its agriculturally suftable salts.

26.4-Chloro-N 2_[(4-methoxy-6-methylpyri m idin-2-y1)a minoca rbonyll -W, N 1 A i methyl- 1,2 benzenedisulfonamide; and its agriculturally suitable salts.

27. (2,2,2-Trifluoroethyi) 2-[[(4,6-dimethoxypyrimidin-2yi)aminocarbonyllaminosulfonyll- benzenesulfonoate; and its agriculturally suitable salts.

28. (2,2,2-Trifluoroethyi) 2-[[(4,6-dimethoxy-1,3,5-triazin-2yi)aminocarbonyi)aminosuifonyll- benzenesulfonoate; and its agriculturally suitable salts.

29. (2,2,2-Trifluoroethyi) 2-[[(4-methoxy-6-methylpyrimidin-2yi)aminocarbonyllaminosuifonyll- benzenesulfonoate; and its agriculturally suitable salts.

30. (2,2,2-Trifluoroethyi) 2-[[(4-methoxy-6-methyi- 1,3,5-triazin-2yi)aminocarbonyll- aminosuifonyllbenzenesuifonoate; and its agriculturally suitable salts.

108 GB 2 057 429 A 108

31. N[(4,6-Dimethylpyrimidin-2-yi)aminocarbonyll-N-ethyi-N-methyi-1,2benzenedis uifonamide; and its agriculturally suitable salts.

32. N-thyl-N'-[(4-methoxy-6-methylpyrimidin-2-yi)aminocarbonyil-N-methyl1,2benzenedisuifonamide; and its agriculturally suitable salts.

33. N'-[(4,6-Dimethoxypyrimidin-2-yi)aminocarbonyilN-ethyiN-methyl-1, 2benzenedisulfonamide; and its agriculturally suitable salts.

34. 4-Ch foro-N-[(4-methoxy-6-methyl- 1,3,5-triazin-2 -yi) a minoca rbonyll-N,N-di m ethyl- 1,2benzenedisuifonamide; and its agriculturally suitable salts.

35. N,N-Dimethyf-N-(([4-methyi-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2yilamin ocarbionyl))- 1,2-benzenedisulfonamide; and its agriculturally suitable salts.

36. N-Methyi-N(l-methylethyi)-N'-[(4,6-dimethoxypyrimidin-2yi)aminocarbonyll-1, 2- benzenedisulfonamide; and its agriculturally suitable salts.

37. N-Methyl-N(l-methylethyi)-N'-[(4-methyl-6-methoxypyrimidin-2yi)aminocarbony i1-1,2- benzenedisuffonamide; and its agriculturally suitable salts.

38. N-Methyl-N(l-methylethyi)-N'-[4-methyi-6-methoxy-1,3,5triazin-2yl)aminocar bonyll-1,2- 15 benzenedisulfonamide; and its agriculturally suitable salts.

39. Compounds of claim 1, substantially as illustrated in the Examples 140 herein.

40. A composition for the control of undesirable vegetation comprising a compound of any of claims 1 -12 or 39 and at least one of (a) a surface-active agent and (b) a solid or liquid diluent.

41. A composition for the control of undesirable vegetation comprising a compound of any of 20 claims 13-38 and at least one of (a) a surface-active agent and (b) a solid or liquid diluent.

42. A composition of claim 40 or 41, substantially as illustrated in Examples 41-51 herein.

43. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of any of claims 1-12 or 39.

44. A method for the control of undesirable vegetation comprising applying to the locus of such 25 undesirable vegetation a herbicidally effective amount of a compound of any of claims 13-38.

45. A method according to claim 43 or 44, substantially as illustrated in the Tests A-E herein.

46. A method for regulating the growth of plants which comprises applying to the locus of such plants an effective but substantially non-phytotoxic amount of a compound of any of claims 1-39 having growth regulant activity.

47. A method for making a compound of claim 1 which comprises reacting together compounds of formulae wherein 35 A is N%R3, OCH2CC13, OCH2CBr3, OCH2C172% or so 2-A S02 N=C=W R 01-11' R 1 and HN-R 9 6 R 5 a 0 R ' OCHRc 1 U[-, where R. is H, Cl, CH,, OCH, or NO, and Rb is H, F or C,_C2 alkyl with 0- 5F and Rc is CH, or CF,. R1 is H, Cl, Br, F, N02, C,-C, alkyl, OCH,, CF., 0 11 k'hd or CH2ORd where Rd 'S Cl-C3 a lkyi, N(CHI, CN, (0) n (0) n 11 11 CH30-Lt12 or Cri,Z) v i C -1.

109 GB 2 057 429 A 109 where n is 0 or 2; R' is H, Cl, F, Br, CH. or OCH 1 3; R2 is Cl-C, alkyl, C3-C4 alkenyl, C,-C, cycloalkyl, CS-C, cycloalkenyl, Cl__C7 cycloalkylalkyl, C,_C, cycloalkyl substituted with 1-2 CH3 groups, C3-C5 alkynyi, C(CHICK (CH2).. CN, where m is 1 or 2, CF2CF2H, CF2CHM, CF2 CHFBr, CF2CHFU3, CH2CF3, CH2CH2OCH3, CH2CH(CHACH3, 5 (CHIOCH3, or OCH3, provided that when R2 is OCH3, R3 is CH3, CHM,)C02R, or CHM,)COMIR,)2, where R7 is H or CH3, and R,'S Cl-C3 alkyl; or R2 'S CH (R 7) or OCHF7 R 9 where R9 is H, CH., Cl, Br or F; R, 'S Cl-C4 alkyl, C3-C4 alkenyl, CH2CH2OCH3, CH2CH(CHJOCH3, (CH2).. CK where m is 1 or 2, CH(R7)C02%, -CH,CF3, or NIR2R, taken together are -N3 P -N 0 or -N provided that when R2 is CF2CHM, CF2CHFBr, CF2CF2H, or CF2CHFU,, then R. iS Cl-4 alkyl; Also provided that when R, is M or N=C=Q.ft cannot be in the 3-positi. o. n.

W is oxygen or sulfur; R5 is H or methyl; R, is X - X N -\/ N - N 0 z oN o r (D-- X1 N N \ Y Y Y 1 and X is H, CH3, CH30 or CH3CH20; Y is Cl, Br, H, Cl-C3 alkyl, CF3, NHCH3, N(CHI, OCH2CF3, OCH3, OCH,CH3, SCH., CH2CM NCH,M, 1 C113 CH2CH2M, CH2C1, N3, OCH2CH=CH2, OCH2C=_CH or O(CH2)p013,., where P is 2 or 3 and 13,0 is CH. or CH.CH2, or 25 Y is CH2C1120CH., CH20CH3, OCH(ROCO2R1 l or OCH(ROCON(RJ2, C0213,1 and CH2C02131,, R7 and R. are as previously defined; and Rll is H or Cl-C3 alkyl; X, is H, OCH3 or CH3; Y1 is H, OCH3, OCH2C3 or CH3, provided that X, and Yl are not both H simultaneously; and 30 Z is N or CH; to obtain a corresponding compound of general formula so 2-A W to SO N-C-N-R 2 0 6 R R@ i41 wherein the substituents are as defined above.

GB 2 057 429 A 110 of formulae

48. A method for making a compound of claim 1 which comprises reacting together compounds f 0 2 A so 2-H Ri/Q R 4 - 1 and SCNR 6 wherein A, R,, W,, R2, R3 and R6 are as defined in claim 47 and R4 is H or CH 3, to obtain a corresponding 5 compound of general formula wherein--- the substituents are as defined above.

0 g2 -A so 2-CNHR 6 R 4 RI R

49. A method for making a compound of claim 1 which comprises performing the reaction:

so 2 -A so 2 -A c 0 2 NHW-R 6 R so 2 N=C=S 1) NaN-R Ri 2) H 3 0 /R 1 R R 1 iv wherein A, R,', R,-R, are as defined in claim 47.

50. A method for making a compound of claim 1 which comprises reacting together so 2 -A R j AR. S02 NH 2 1 to obtain a corresponding compound of formula wherein A, R, and R' are as defined in claim 47 X2 is C], Br, methyl, ethyl or CF3 Y2 is H, Cl, Br, Methyl, ethyl or CF3 Z is N or CH; followed by converting X2 into GR12 where R12'S methyl, ethyl, - X2 and O=C=N C) z N:

Y 2 so 2 A 0 d 2 01 ( j so 2 MiCNH z !i - N Ri R CH3 1 -(_;H U02CH3 Y 2 1 AI ill GB 2 057 429 A ill or -CH2CO2CH, by a nucleophilic displacement, and converting Y2, if desired, into 0Me or OEt by a nucleophilic displacement.

51. A method for making a compound of claim 1 which comprises performing the reaction SO 2 A _ + N S m 2 z so 2 N=C NH -(D N:::/ BI or BBr X 1 Y 1 so 2 A S-B 9 _0 Z RP( so 2 N=C - NH - X N:/Y 1 wherein A, R,, X, and Z are as defined in claim 47 and B is C,-C,, alkyl; CH2CH2OCH3; CH2CH2OCH2CH3; CH2CH2CH2OCH,; CHA CH-Q; 1 CH3 where Q'S C02-C1-, alkyl, 0 CH3 0 11 / 11 11 -CN -UNkC,-3 alky02, -ummktl-k,3 alkyO, OCH, 0 phenyl, phenyl substituted with chlorine, CN, C2-4 alkenyl, C24 alkynyi, - OR,,, where R,', is 1 10 C,_C4 alkyl, -CH20CH2CH2OCH3 or -CH20CH2dH2DCH2CH3 and M is an alkali or alkaline earth metal.

52. Methods for making compounds of claim 1, substantially as illustrated in Examples 1 to 40 herein.

53. A compound of claim 1 selected from SO 2 NR 2 R 3 W 0.9 0m2L,"-km-^6 1 R 4 R 5 wherein R, is H, Cl, Br, F, Cl-C3 alkyl, N02, OCH3, CF3, NH2, N(CHI, CN, or SOnCH3, where n is 0, 1 or 2; R2 is Cl-C, alkyl, C3-C4 alkenyi, C,-C, cycloalkyl, C57---C,cycloalkenyl, C3-Cl cycloalkenyl substituted with 1-2 CH3 groups, C(CH),CK (CH2),,CN, where m is 1 or 2; CH2CH2OCH3, 20 CH2CH(CH3)OCH3, (CH2)30CH3, CHR7C02R. or CHR7CON(RJ21 where R, is H or CH3 and R. is where 25 R9 is H, CH3, Cl, Br or F; R3 'S C1-4 alkyl; or Cl-C3 alkyl, or R2 is OCH,, provided that when R2 is OCH3, R3 is CH3; -Q or CHR7.-Q R 9 112 GB 2 057 429 A 112 R3 'S C3-C4 alkenyi, CH2C1-120CH, CH,CH(CH,)OCH,, or (CH2) CN, where m is 1 or 2, or CHR-,CO,R,, provided that R2 = R3; or NR2R3 taken together are -N3 -N 0 or \--i R4 and IR,, are independently H or CH, but R4 and R, cannot both be CH3; R, is N 7 X N- X N-N z / \-X 1 N=.1 Y1 Y 1 wherein X is H, CH3, CH30 or CH3CH20; 10 Y is H, CH3, CF3, NI-ICI-13, N(C1-11, OCH,CF3, OCH, 0C21-1, SCH3 or O(C1-12)p011,, where p is 2 or 3 and R,. is CH3 or C21-l., or Y is CH2CH2OCH3, C1-1,0CH31 OCHR7CO^ or OCHR7CON(RJ,; X, is H, OCH3 or CH3;.Y1 is H, OCH3, OCH2CH3, or CH3, provided that X, and Y1 are not both H simultaneously; Z is N or CH; and W is 0 or S.

Y - AL 11 Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981. Published by the Patent Office. 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtainecl 4 1